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<cml xmlns="http://www.xml-cml.org/schema"><module role="metadata"><FILENO xmlns="">b201228f</FILENO><PAPERTYPE xmlns="">article</PAPERTYPE><JOURNAL xmlns=""><NAME>P1</NAME><YEAR>2002</YEAR><VOLUME/><ISSUE>13</ISSUE><PAGES>1581-1587</PAGES></JOURNAL></module><module role="title">Carotenoids and related <molecule title="polyenes" role="chemical"><link title="1" to="cit1"/></molecule>. Part 8. Total synthesis of optically active <molecule title="mytiloxanthin" role="chemical"/> applying the stereoselective rearrangement of tetrasubstituted <molecule title="epoxide" role="chemical"/><XREF ID="fn1" TYPE="FOOTNOTE_MARKER" xmlns=""/></module><module role="authorList"><AUTHOR ID="1" xmlns=""><NAME>Chisato<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR ID="2" xmlns=""><NAME>Yumiko<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR ID="3" xmlns=""><NAME>Masayoshi<SURNAME>Ito</SURNAME></NAME></AUTHOR></module><module role="abstract">Biomimetic synthesis of  <molecule ref="chem1" title="1"><name>mytiloxanthin</name></molecule> was accomplished with stereoselective rearrangement of the tetrasubstituted <molecule title="epoxide" role="chemical"/> <molecule ref="chem5" title="5"/> as a key reaction. This is the first total synthesis of optically active all-<IT xmlns="">E</IT> <molecule title="mytiloxanthin" role="chemical"/> <molecule ref="chem1" title="1"/>.</module><module role="body">
		<module role="introduction">
			<module role="para"><module role="container"> </module><molecule ref="chem1" title="1"><name>Mytiloxanthin</name></molecule><module role="container">, with a unique </module><molecule title="cyclopentyl enolic [beta]-diketone" role="chemical"/><module role="container"> group conjugated to a </module><molecule title="polyene" role="chemical"/><module role="container"> chain, was first isolated from <IT xmlns="">Mytilus californianus</IT> by Scheer in 1940.<REF ID="cit2" TYPE="P" xmlns="">2</REF> Its structure and synthesis of the 9<IT xmlns="">Z</IT>-isomer were reported by Weedon's group,<REF ID="cit3" TYPE="P" xmlns="">3</REF> they developed the new synthetic route to </module><molecule title="polyene [beta]-diketones" role="chemical"/><module role="container"> using Claisen type condensation between </module><molecule title="polyene" role="chemical"/><module role="container"> esters and </module><molecule title="methyl ketones" role="chemical"><link title="4" to="cit4"/></molecule><module role="container">. The absolute configuration was determined by Maoka and Fujiwara in 1996. The </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> end group of </module><molecule title="mytiloxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem1" title="1"><link title="3" to="cit3"/></molecule><module role="container"> is believed to be formed in Nature from the </module><molecule title="epoxide" role="chemical"/><module role="container"> end group of </module><molecule title="5,6-epoxy" role="chemical"/><module role="container"> carotenoids such as </module><molecule title="halocynthiaxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem2" title="2"/><module role="container"> by cleavage of the </module><molecule title="oxirane" role="chemical"/><module role="container"> ring at the C-5 position and successive ring contraction (a </module><molecule title="pinacolic" role="chemical"/><module role="container"> rearrangement)
(Scheme 1, route <IT xmlns="">a</IT>).</module></module>
			
			<module role="para"><module role="container">We found<REF ID="cit5" TYPE="P" xmlns="">5</REF> that the acyclic-tetrasubstituted olefinic compounds and the </module><molecule title="cyclopentyl ketone" role="chemical"/><module role="container"> were derived by Lewis acid-promoted stereoselective rearrangement of </module><molecule title="epoxy" role="chemical"><link title="1,6" to="cit1 cit6"/></molecule><module role="container"> compounds. Then, the biomimetic total synthesis of </module><molecule title="crassostreaxanthin" role="chemical"/><module role="container"> B </module><molecule ref="chem3" title="3"/><module role="container"> possessing the acyclic-tetrasubstituted olefinic end group was achieved using this rearrangement reaction.</module></module>
			<module role="para"><module role="container">In a previous communication,<REF ID="cit7" TYPE="P" xmlns="">7</REF> we reported the first total synthesis of  </module><molecule ref="chem1" title="1"><name>mytiloxanthin</name></molecule><module role="container"> which includes the new construction of conjugated </module><module role="container"> </module><molecule ref="chem10a chem10b" title="10a,b"><name>[beta]-diketones</name></molecule><module role="container"> through the </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> compound </module><molecule ref="chem8" title="8"/><module role="container"> (Scheme 2), prepared by application of the stereoselective rearrangement of </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5" title="5"/><module role="container">. The present paper is concerned with a full account of the experiments.</module></module>
			
		</module>
		<module role="results">
			<module role="para"><module role="container">It has been previously reported<REF ID="cit5b" TYPE="P" xmlns="">5<IT>b</IT></REF> that </module><molecule title="OEt2-treatment" role="chemical"/><module role="container"> of the </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem4" title="4"/><module role="container"> (Scheme 2) with the </module><molecule title="acetoxy ethyl" role="chemical"/><module role="container">group at the C-6 position resulted in a very slow reaction and in a low-</module><action title="yield" role="cml:yield"/><module role="container">formation of the C-5 diastereomer </module><molecule ref="chem6" title="6"/><module role="container"> instead of the desired compound </module><molecule ref="chem7" title="7"/><module role="container">. Efficient preparation of </module><molecule ref="chem7" title="7"/><module role="container"> was obtained from the investigation of other Lewis acids with an </module><molecule title="aminium" role="chemical"/><module role="container"> salt. Thus, treatment of the </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem4" title="4"/><module role="container"> with </module><molecule title="tris(4-bromophenyl)aminium hexachloroantimonate" role="chemical"/><module role="container"> </module><molecule ref="chem9" title="9"><link title="8" to="cit8"/></molecule><module role="container"> in </module><molecule title="CH2Cl2"/><module role="container">was found to</module><action title="afford" role="cml:give"/><module role="container"> </module><molecule ref="chem7" title="7"/><module role="container">in reasonable</module><action title="yield" role="cml:yield"/><module role="container">(69%) (Scheme
2). In order to accomplish the biomimetic synthesis of </module><molecule ref="chem1" title="1"/><module role="container"> in an analogous manner to the successful synthesis of </module><molecule ref="chem3" title="3"/><module role="container">, the </module><molecule title="acetoxy" role="chemical"/><module role="container"> group at the C-3 position in </module><molecule ref="chem4" title="4"/><module role="container"> was replaced by the </module><molecule title="tert-butyldimethylsilyl" role="chemical"/><module role="container"> (TBS) </module><molecule title="ether" role="chemical"/><module role="container"> leading to </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5" title="5"/><module role="container">. The synthetic route of </module><molecule title="mytiloxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem1" title="1"/><module role="container"> was therefore planned through conversion of </module><molecule ref="chem5" title="5"/><module role="container"> to the </module><molecule title="cyclopentyl ketone" role="chemical"/><module role="container"> </module><molecule ref="chem8" title="8"/><module role="container"> and subsequent construction of </module><molecule title="enolic [beta]-diketone" role="chemical"/><module role="container"> as shown in Scheme 2.</module></module>
			<module role="para"><module role="container">Starting from the previously prepared optically active <REF ID="cit1" TYPE="P" xmlns="">1</REF>
				</module><molecule ref="chem11" title="11"><name>alcohol</name></molecule><module role="container">(Scheme 3), acetylation followed by epoxidation with MCPBA</module><action title="gave" role="cml:give"/><module role="container"> </module><module role="container"> </module><molecule ref="chem5a chem5b" title="5a,b"><name>epoxides</name></molecule><module role="container"> (</module><module role="balancedBrackets"><molecule ref="chem5a" title="5a"/><module role="container">: 26% from </module><molecule ref="chem11" title="11"/><module role="container">; </module><molecule ref="chem5b" title="5b"/><module role="container">: 48% from </module><molecule ref="chem11" title="11"/></module><module role="container">), in which the relative configurations between the </module><molecule title="silyloxy" role="chemical"/><module role="container"> and </module><molecule title="epoxy" role="chemical"/><module role="container"> groups were confirmed by <SP xmlns="">1</SP>H NMR.<REF ID="cit9" TYPE="P" xmlns="">9</REF> The undesired isomer </module><molecule ref="chem5b" title="5b"/><module role="container"> was returned to the tetrasubstituted </module><molecule title="olefin" role="chemical"/><module role="container"> </module><molecule ref="chem12" title="12"/><module role="container"> by the following deepoxidation procedure. Treatment of </module><molecule ref="chem5b" title="5b"/><module role="container"> with </module><molecule title="TMSCl"/><module role="container"> and </module><molecule title="NaI"/><module role="container"> in dry </module><molecule title="acetonitrile" role="chemical"><link title="10" to="cit10"/></molecule><module role="container">followed by silylation</module><action title="gave" role="cml:give"/><module role="container"> </module><molecule ref="chem12" title="12"/><module role="container"> in 60% yield. Reaction of </module><molecule title="anti-epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5a" title="5a"/><module role="container"> with </module><molecule title="aminium" role="chemical"/><module role="container"> salt </module><molecule ref="chem9" title="9"/><action title="provided" role="cml:provide"/><module role="container"> the desired </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> compound </module><molecule ref="chem8" title="8"/><module role="container"> (63%) and its deprotected </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem13" title="13"/><module role="container">(30%) which was easily resilylated to</module><action title="give" role="cml:give"/><module role="container"> </module><molecule ref="chem8" title="8"/><module role="container"> (89%). Consequently, the </module><molecule title="cyclopentyl ketone" role="chemical"/><module role="container"> </module><molecule ref="chem8" title="8"/><module role="container"> was synthesized by the stereoselective rearrangement of </module><molecule ref="chem5a" title="5a"/><module role="container"> in high yield. The structure of </module><molecule ref="chem8" title="8"/><module role="container"> was determined from the following spectral data. Its IR absorption showed a new </module><molecule title="carbonyl" role="chemical"/><module role="container"> frequency at 1699 cm<SP xmlns="">-1</SP>. In its <SP xmlns="">1</SP>H NMR spectrum, the </module><molecule title="methylene" role="chemical"/><module role="container"> signal of the C-7 position appeared at <IT xmlns="">[delta]</IT>
2.75 (t), further downfield than the corresponding signal [<IT xmlns="">[delta]</IT> 2.01 (2H, m)] of </module><molecule ref="chem5a" title="5a"/><module role="container">, in addition, </module><molecule title="proton" role="chemical"/><module role="container"> signals on the </module><molecule title="cyclopentane" role="chemical"><link title="5b" to="cit5b"/></molecule><module role="container"> ring were observed analogous to results reported previously.</module></module>
			
			<module role="para"><module role="container">Reduction of </module><molecule ref="chem8" title="8"/><module role="container"> with </module><molecule title="NaBH4"/><module role="container"> followed by protection of the resulting </module><molecule title="hydroxy" role="chemical"/><module role="container"> group with </module><molecule title="p-methoxybenzyloxymethyl" role="chemical"/><module role="container"> (PMBM) </module><molecule title="chloride" role="chemical"><link title="11" to="cit11"/></molecule><action title="gave" role="cml:give"/><module role="container"> compound </module><molecule ref="chem14" title="14"/><module role="container"> (62% from </module><molecule ref="chem8" title="8"/><module role="rbracket"/><module role="container">), which was reduced with LAH to</module><action title="provide" role="cml:provide"/><module role="container">the </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem15" title="15"/><module role="container"> (99%). This was subjected to oxidation with </module><molecule title="o-iodoxybenzoic acid" role="chemical"><link title="12" to="cit12"/></molecule><module role="container">(IBX) to</module><action title="yield" role="cml:yield"/><module role="container">the </module><molecule title="aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem16" title="16"/><module role="container"> (93%), which was reacted with </module><molecule title="vinyllithium" role="chemical"/><module role="container"> prepared from the </module><molecule title="vinyl bromide" role="chemical"/><module role="container"> </module><molecule ref="chem17" title="17"><link title="13" to="cit13"/></molecule><module role="container"> and Bu<SP xmlns=""><IT>t</IT></SP>Li followed by oxidation with IBX to</module><action title="provide" role="cml:provide"/><module role="container">the </module><molecule title="ketone" role="chemical"/><module role="container"> </module><molecule ref="chem18" title="18"/><module role="container"> (60% from </module><molecule ref="chem16" title="16"/><module role="rbracket"/><module role="container">). Its structure
was confirmed by IR (<IT xmlns="">[nu]</IT> 1669 cm<SP xmlns="">-1</SP>) and <SP xmlns="">1</SP>H NMR data [<IT xmlns="">[delta]</IT> 6.53 (1H, tq-like, <IT xmlns="">J</IT> 5, 1, 10-H), 4.26 (2H, m, 11-</module><molecule title="H2"/><module role="rbracket"/><module role="container">)]. Deprotection of the PMBM group in </module><molecule ref="chem18" title="18"><link title="11b" to="cit11b"/></molecule><module role="container"> with DDQ</module><action title="gave" role="cml:give"/><module role="container"> the </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem19" title="19"/><module role="container"> (88%), which was treated with </module><molecule title="DMSO" role="chemical"/><module role="container"> and </module><molecule title="Ac2O"/><module role="container">to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="enolic [beta]-diketone" role="chemical"/><module role="container"> </module><molecule ref="chem20" title="20"/><module role="container"> (36%) and the </module><molecule title="acetate" role="chemical"/><module role="container"> </module><molecule ref="chem21" title="21"/><module role="container"> (33%). Attempts to prepare </module><molecule ref="chem20" title="20"/><module role="container"> from </module><molecule ref="chem19" title="19"/><module role="container"> under other oxidation conditions (<IT xmlns="">e.g.</IT>, </module><molecule title="DMSO-oxalyl chloride" role="chemical"/><module role="container">, DMSO-TFAA, DMSO-</module><molecule title="SO3·Py"/><module role="container">, NMO-TPAP and IBX) were</module><action title="unsuccessful" role="cml:unsuccessful"/><module role="container">. The <SP xmlns="">1</SP>H NMR spectrum of </module><molecule ref="chem20" title="20"/><module role="container"> had a broad
one-proton signal at <IT xmlns="">[delta]</IT> 16.15 and a sharp one-proton resonance at <IT xmlns="">[delta]</IT> 5.81. In addition, its IR spectrum showed an absorption at 1583 cm<SP xmlns="">-1</SP> exhibiting the presence of a strongly hydrogen-bonded </module><molecule title="carbonyl" role="chemical"/><module role="container"> group. These spectral data confirmed the presence of a completely </module><molecule title="enolic [beta]-diketone" role="chemical"/><module role="container"> structure. The structure of </module><molecule ref="chem21" title="21"/><module role="container"> was revealed by the following <SP xmlns="">1</SP>H NMR data [an </module><molecule title="acetoxy methyl" role="chemical"/><module role="container"> signal appeared at <IT xmlns="">[delta]</IT> 2.14 (3H, s) and a </module><molecule title="proton" role="chemical"/><module role="container"> signal (<IT xmlns="">[delta]</IT> 4.23) due to C-6 shifted downfield compared to the corresponding signal (<IT xmlns="">[delta]</IT> 4.04) of </module><molecule ref="chem19" title="19"/><module role="container">].</module></module>
			<module role="para"><module role="container">Unfortunately, direct conversion of </module><molecule ref="chem20" title="20"/><module role="container"> into the  </module><molecule ref="chem10a" title="10a"><name>C15-[beta]-diketone aldehyde</name></molecule><module role="container"> (Scheme 2) by deprotection of the </module><molecule title="allylic" role="chemical"/><module role="container"> TBS group and subsequent oxidation of the resulting </module><molecule title="alcohol" role="chemical"/><module role="container"> using several reagents (IBX, </module><molecule title="MnO2"/><module role="container">, <IT xmlns="">etc</IT>.) was</module><action title="unsuccessful" role="cml:unsuccessful"/><module role="container">, probably due to the instability of the </module><molecule title="[beta]-diketone" role="chemical"/><module role="container"> part. Thus, after protection of the </module><molecule title="[beta]-diketone" role="chemical"/><module role="container"> moiety in </module><molecule ref="chem20" title="20"/><module role="container"> by acetylation, the resulting </module><molecule title="acetate" role="chemical"/><module role="container"> </module><molecule ref="chem22" title="22"/><module role="container">was partly deprotected with TBAF to</module><action title="give" role="cml:give"/><module role="container"> the </module><molecule title="allylic alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem23" title="23"/><module role="container"> (92%) which was oxidized with IBX followed by removal of another TBS group with </module><molecule title="HF"/><module role="container">to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="C15-aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem10b" title="10b"/><module role="container"> (55% from </module><molecule ref="chem23" title="23"/><module role="rbracket"/><module role="container">) as shown in Scheme 4. Its <SP xmlns="">1</SP>H NMR spectrum showed no signal from the TBS group but it did display a pair of doublets attributable to the 11-H (<IT xmlns="">[delta]</IT> 10.17, d, <IT xmlns="">J</IT> 7.5) and 10-H (<IT xmlns="">[delta]</IT> 6.37, d, <IT xmlns="">J</IT> 7.5).</module></module>
			
			<module role="para"><module role="container">The Wittig reaction of </module><molecule ref="chem10b" title="10b"/><module role="container"> with the  salt </module><molecule ref="chem25" title="25"><name>C10-phosphonium</name><link title="14" to="cit14"/></molecule><module role="container"> in the presence of </module><molecule title="KOH"/><module role="container">as a base in a</module><substance title="mixture" role="cml:substance"/><module role="container"> of </module><molecule title="water" role="chemical"/><module role="container"> and </module><molecule title="propan-2-ol" role="chemical"/><action title="gave" role="cml:give"/><module role="container"> condensed products which, after </module><molecule title="acid" role="chemical"/><module role="container">hydrolysis,</module><action title="provided" role="cml:provide"/><module role="container"> an isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> of </module><molecule title="C25-apocarotenals" role="chemical"/><module role="container"> </module><molecule ref="chem26" title="26"/><module role="container"> (92% from </module><molecule ref="chem10b" title="10b"/><module role="rbracket"/><module role="container">). Investigations of alternative conditions (<IT xmlns="">e.g.</IT>, </module><molecule title="NaOMe-MeOH"/><module role="container">, Bu<SP xmlns=""><IT>n</IT></SP>Li-CH<SB xmlns="">2</SB>Cl<SB xmlns="">2</SB>-THF) for optimization of this condition resulted in the formation of an unexpected complex</module><substance title="mixture" role="cml:substance"/><module role="container">. This is presumably owing to the presence of the conjugated </module><molecule title="[beta]-diketone" role="chemical"/><module role="container"> moiety in the molecule. It was notable that </module><molecule title="KOH"/><module role="container"> was the best base in the condensation of the conjugated </module><molecule title="polyenes" role="chemical"/><module role="container"> including the </module><molecule title="[beta]-diketone" role="chemical"/><module role="container">part. Finally, the isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> </module><molecule ref="chem26" title="26"/><module role="container"> was condensed with the </module><molecule title="acetylenic" role="chemical"/><module role="container"> C<SB xmlns="">15</SB>-Wittig salt </module><molecule ref="chem27" title="27"><link title="15" to="cit15"/></molecule><module role="container"> in the presence of </module><molecule title="KOH"/><module role="container"> in </module><molecule title="propan-2-ol" role="chemical"/><module role="container">at 0 °C to</module><action title="yield" role="cml:yield"/><module role="container">the products (30%), a part of which</module><action title="was separated by" role="cml:separated"/><module role="container">repeated preparative HPLC (PHPLC) in the dark to</module><action title="afford" role="cml:give"/><module role="container"> all-<IT xmlns="">E</IT> </module><molecule title="mytiloxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem1" title="1"/><module role="container">, 9<IT xmlns="">Z</IT>-isomer </module><molecule ref="chem28" title="28"/><module role="container">, </module><molecule title="9Z,11Z-one" role="chemical"/><module role="container"> </module><molecule ref="chem29" title="29"/><module role="container"> and unidentified isomers. Three isomers (</module><module role="balancedBrackets"><molecule ref="chem1" title="1"/><module role="container">, </module><molecule ref="chem28" title="28"/><module role="container"> and </module><molecule ref="chem29" title="29"/></module><module role="container">) were respectively obtained in pure form (all-<IT xmlns="">E</IT>
				</module><molecule ref="chem1" title="1"/><module role="container">-9<IT xmlns="">Z</IT>
				</module><molecule ref="chem28" title="28"/><module role="container">-9<IT xmlns="">Z</IT>,11<IT xmlns="">Z</IT>
				</module><molecule ref="chem29" title="29"/><module role="container">
				=
				<IT xmlns="">ca.</IT>
1 : 1 : 1). Spectral data (UV-VIS, <SP xmlns="">1</SP>H NMR and CD) of synthetic </module><molecule title="mytiloxanthins" role="chemical"/><module role="container"> (all-<IT xmlns="">E</IT> and 9<IT xmlns="">Z</IT>-isomers) were in good agreement with those of natural specimens, respectively.<REF ID="cit4" TYPE="P" xmlns="">4</REF> Their configurations were confirmed from 2D-nuclear Overhauser enhancement spectroscopy (NOESY) experiments in <SP xmlns="">1</SP>H NMR spectra (see Experimental section). 9<IT xmlns="">Z</IT>,11<IT xmlns="">Z</IT>-Stereochemistry in </module><molecule ref="chem29" title="29"/><module role="container"> was determined by <SP xmlns="">1</SP>H NMR data in comparison with those<REF ID="cit16" TYPE="P" xmlns="">16</REF> of 9'<IT xmlns="">Z</IT>,11'<IT xmlns="">Z</IT>-isomer of </module><molecule title="halocynthiaxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem2" title="2"/><module role="container"> skeletal compound. This is the first biomimetic total synthesis of optically active all-<IT xmlns="">E</IT> </module><molecule title="mytiloxanthin" role="chemical"/><module role="container"> </module><molecule ref="chem1" title="1"/><module role="container"> by application of the stereoselective rearrangement of the </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5a" title="5a"/><module role="container"> with </module><molecule title="aminium" role="chemical"/><module role="container">
salt </module><molecule ref="chem9" title="9"/><module role="container">.</module></module>
		</module>
		<module role="experimental">
			<module role="para"><module role="container">UV-VIS spectra were recorded on a JASCO Ubest-55 instrument for </module><molecule title="ethanol" role="chemical"/><action title="solution" role="cml:solution"/><module role="container">s unless otherwise stated. IR spectra were measured on a Perkin Elmer FT-IR spectrometer, model Paragon 1000, for </module><molecule title="chloroform" role="chemical"/><action title="solution" role="cml:solution"/><module role="container">s. <SP xmlns="">1</SP>H NMR spectra at 300 or 500 MHz were determined on a Varian Gemini-300 or a Varian VXR-500 superconducting FT-NMR spectrometer, respectively, for </module><molecule title="deuteriochloroform" role="chemical"/><action title="solution" role="cml:solution"/><module role="container">s (</module><module role="lbracket"/><molecule title="tetramethylsilane" role="chemical"/><module role="container"> as internal reference). <IT xmlns="">J</IT>-Values are</module><action title="give" role="cml:give"/><module role="container">n in Hz. NMR assignments are</module><action title="give" role="cml:give"/><module role="container">n using the carotenoid numbering system. Mass spectra were taken on a Hitachi M-4100 spectrometer. Optical rotations were measured on a JASCO DIP-181 polarimeter ([<IT xmlns="">[alpha]</IT>]<SB xmlns="">D</SB>-values are in units of 10<SP xmlns="">-1</SP> deg cm<SP xmlns="">2</SP> g<SP xmlns="">-1</SP>). CD spectra were measured on a Shimadzu-AVIV 62A </module><molecule title="DS"/><module role="container"> circular dichroism spectrometer.</module></module>
			<module role="para"><module role="container">Column chromatography (CC) was performed on </module><molecule title="silica" role="chemical"/><module role="container"> gel (Merck Art. 7734). Short-column chromatography (SCC) was carried out on </module><molecule title="silica" role="chemical"/><module role="container"> gel (Merck Art. 7739) under reduced pressure. Preparative TLC (PTLC) was conducted on </module><molecule title="silica" role="chemical"/><module role="container"> gel </module><property dictRef="osc:nature"><scalar dictRef="osc:solidstate" dataType="xsd:string">plates</scalar></property><module role="container"> (Merck </module><molecule title="silica" role="chemical"/><module role="container"> gel 60F<SB xmlns="">254</SB> precoated </module><property dictRef="osc:nature"><scalar dictRef="osc:solidstate" dataType="xsd:string">plates</scalar></property><module role="container">, </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:conc" units="oscUnits:unknown">0.5</scalar></property><module role="container"> thickness). Low-pressure CC was performed on a Yamazen Low Pressure </module><property dictRef="osc:nature"><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">Liquid</scalar></property><module role="container"> Chromatography System using a Lobar column (Merck LiChroprep </module><molecule title="Si"/><module role="container"> 60). Analytical and PHPLC were carried out on Shimadzu LC-6A, or Waters 510 instruments with UV-VIS detectors.</module></module>
			<module role="para"><module role="container">Standard work-up means that the organic layers or</module><action title="extract" role="cml:extract"/><module role="container">s were finally</module><action title="washed" role="cml:washed"/><module role="container"> with </module><molecule title="brine" role="chemical"/><module role="container">, </module><property state="cml:dry"/><module role="container"> over </module><property state="cml:anhydrous"/><module role="container"> </module><molecule title="sodium sulfate" role="chemical"/><module role="container"> (</module><molecule title="Na2SO4"/><module role="container">), filtered and </module><property state="cml:concentrated"/><module role="container"> <IT xmlns="">in vacuo</IT> below </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">30.0</scalar></property><module role="container"> using a rotary evaporator. All operations were carried out under </module><molecule title="nitrogen" role="chemical"/><module role="container"> or </module><molecule title="argon" role="chemical"/><module role="container">. </module><molecule title="Hexane" role="chemical"/><module role="container"> refers to </module><molecule title="n-hexane" role="chemical"/><module role="container">.</module></module>
			<DIV xmlns=""><HEADER>Rearrangement of the  <molecule ref="chem4" title="4" xmlns="http://www.xml-cml.org/schema"><name>epoxide</name></molecule> with  salt <molecule ref="chem9" title="9" xmlns="http://www.xml-cml.org/schema"><name>aminium</name></molecule></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of </module><molecule ref="chem4" title="4"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">142.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.5</scalar></property></module><module role="container">) in </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.5</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container"> salt </module><molecule ref="chem9" title="9"><name>aminium</name><link title="8" to="cit8"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">8.17</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.01</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">2.0</scalar></property><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the reaction</module><substance title="mixture" role="cml:substance"/><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 2 : 3) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> compound </module><molecule ref="chem7" title="7"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. Spectral data (IR and <SP xmlns="">1</SP>H NMR) of this compound were in agreement with those of our previous report.<REF ID="cit5b" TYPE="P" xmlns="">5<IT>b</IT></REF></module></module>
			</DIV>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem11" title="11"><name>alcohol</name><link title="1" to="cit1"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:g">11.9</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mol">0.04</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> Py (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">20.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="Ac2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">15.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">16.0</scalar></property><module role="container">. The</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 9) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="acetate" role="chemical"/><module role="container"> </module><molecule ref="chem12" title="12"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; [<IT xmlns="">[alpha]</IT>]26D
					-42.6 (<IT xmlns="">c</IT> 1.22, </module><molecule title="MeOH"/></module><module role="container">); <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1732</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.06</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.89</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.02</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.04</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.44</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>,
<peak><quantity type="shift"><value><point>1.61</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.65</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.99</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>9</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.05</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.11</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>7</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.34</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">dt</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value> and <value><point>8.5</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>3.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.99</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>8.5</point></value>, <value><point>8</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem12" title="12"><name>2-[(4R)-4-tert-Butyldimethylsilyloxy-2,6,6-trimethylcyclohex-1-enyl]ethyl acetate</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns="">2-[(1<IT>S</IT>,4<IT>S</IT>,6<IT>R</IT>)- and   and </HEADER>
				<module role="para"><module role="container">A</module><action title="solution" role="cml:solution"/><module role="container"> of MCPBA (72%, </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">552.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">2.29</scalar></property><module role="rbracket"/><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">to an ice-cooled</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem12" title="12"><name>acetate</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">600.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">1.76</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">). After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="Et2O"/><module role="container">and</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 1% </module><molecule title="Na2S2O3"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><module role="container">solvent</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 5) followed by low-pressure CC (</module><module role="lbracket"/><molecule title="Et2O-benzene" role="chemical"/><module role="container">, 1 : 19) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="anti-epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5a" title="5a"/><module role="container">  and the <IT xmlns="">syn</IT>- </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5b" title="5b"/><module role="container">  as </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar></property><module role="container"> oils, respectively.</module></module>
				<reactionScheme><HEADER xmlns=""> </HEADER><module role="para"><module role="container">[<IT xmlns="">[alpha]</IT>]22D
						-10.0 (<IT xmlns="">c</IT> 1.00, </module><molecule title="MeOH"/><module role="rbracket"/><module role="container">); <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1733</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.03</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.03</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.15</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.18</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value> and <value><point>9.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.33</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.44</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value>, <value><point>3.5</point></value> and <value><point>1.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.64</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>7.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.01</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">7-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.04</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.19</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value>, <value><point>5</point></value> and <value><point>1.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>3.77</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.15</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">8-H<SB>2</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				<reaction role="overallReaction"><productList><product><molecule ref="chem5a" title="5a"><name>anti-Epoxide</name></molecule></product></productList></reaction></reactionScheme>
				<reactionScheme><HEADER xmlns=""> </HEADER><module role="para"><module role="container">[<IT xmlns="">[alpha]</IT>]22D
						-30.0 (<IT xmlns="">c</IT> 1.00, </module><molecule title="MeOH"/><module role="rbracket"/><module role="container">); <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1733</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.03</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.06</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.12</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value>, <value><point>4</point></value> and <value><point>2</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.28</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.51</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.81</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>9.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.96</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">7-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.00</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value>, <value><point>7</point></value> and <value><point>1.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.03</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.75</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.07</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">8-H<SB>2</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				<reaction role="overallReaction"><productList><product><molecule ref="chem5b" title="5b"><name>syn-Epoxide</name></molecule></product></productList></reaction></reactionScheme>
			<reaction role="overallReaction"><productList><product><molecule ref="chem5a" title="5a"><name>(1R,4S,6S)-4-tert-Butyldimethylsilyloxy-2,2,6-trimethyl-7-oxabicyclo[4.1.0]heptan-1-yl]ethyl acetate</name></molecule></product><product><molecule ref="chem5b" title="5b"/></product></productList></reaction></reactionScheme>
			<DIV xmlns=""><HEADER>Conversion of  <molecule ref="chem5b" title="5b" xmlns="http://www.xml-cml.org/schema"><name>epoxide</name></molecule> to alkene <molecule ref="chem12" title="12" xmlns="http://www.xml-cml.org/schema"/></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of </module><molecule title="NaI"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:g">1.35</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">9.0</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="acetonitrile" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">10.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="TMSCl"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.56</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">4.5</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">for a few minutes. To this</module><substance title="mixture" role="cml:substance"/><action title="was added" role="cml:added"/><module role="container">a</module><action title="solution" role="cml:solution"/><module role="container"> of the </module><molecule title="epoxide" role="chemical"/><module role="container"> </module><molecule ref="chem5b" title="5b"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:g">1.07</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">3.0</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="Et2O"/><module role="container">and</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 1% </module><molecule title="Na2S2O3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><module role="container">solvent</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="alcohol" role="chemical"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. To a</module><action title="solution" role="cml:solution"/><module role="container"> of the </module><molecule title="alcohol" role="chemical"/><module role="container"> (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">542.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">2.4</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="Et3N"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.64</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">4.8</scalar></property></module><module role="container">), DMAP (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">586.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">4.8</scalar></property></module><module role="container">) and a</module><action title="solution" role="cml:solution"/><module role="container"> of TBSCl (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">433.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">2.9</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">3.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">15.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 9) to</module><action title="yield" role="cml:yield"/><molecule ref="chem12" title="12"/><module role="container"> (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">611.0</scalar></property><module role="container">, 75%; 60% from </module><molecule ref="chem5b" title="5b"/></module><module role="container">) as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. Spectral data of this compound were identical with those of </module><molecule ref="chem12" title="12"/><module role="container"> derived from </module><molecule ref="chem11" title="11"/><module role="container"> in this paper.</module></module>
			</DIV>
			<DIV xmlns=""><HEADER>Rearrangement of  <molecule ref="chem5a" title="5a" xmlns="http://www.xml-cml.org/schema"><name>epoxide</name></molecule> by  salt <molecule ref="chem9" title="9" xmlns="http://www.xml-cml.org/schema"><name>aminium</name></molecule></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem5a" title="5a"><name>epoxide</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">178.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.5</scalar></property></module><module role="container">) in </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">4.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container"> salt </module><molecule ref="chem9" title="9"><name>aminium</name><link title="8" to="cit8"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">42.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.05</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the reaction</module><substance title="mixture" role="cml:substance"/><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 3 : 17 [~~] </module><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 5) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> compound </module><molecule ref="chem8" title="8"/><module role="container">  and the deprotected compound </module><molecule ref="chem13" title="13"/><module role="container">  as </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar></property><module role="container"> oils, respectively.</module></module>
				<DIV><HEADER> compound <molecule ref="chem8" title="8" xmlns="http://www.xml-cml.org/schema"><name>Cyclopentyl</name></molecule></HEADER><module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">[<IT xmlns="">[alpha]</IT>]22D
						+10.0 (<IT xmlns="">c</IT> 1.00, </module><molecule title="MeOH"/><module role="rbracket"/><module role="container">); <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1736</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1699</point></value></quantity> (<quantity type="comment">C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.82</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.14</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.29</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.44</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>3</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.66</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.90</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>7.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.01</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.71</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>8</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.75</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6.5</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.32</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">td</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6.5</point></value> and <value><point>2</point></value>, <value><point>8</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.35</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				</DIV>
				<DIV><HEADER>Deprotected compound <molecule ref="chem13" title="13" xmlns="http://www.xml-cml.org/schema"/></HEADER><module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">[<IT xmlns="">[alpha]</IT>]23D
						+5.00 (<IT xmlns="">c</IT> 1.00, </module><molecule title="MeOH"/><module role="rbracket"/><module role="container">); <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3612</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3468</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1736</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1701</point></value></quantity> (<quantity type="comment">C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.81</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.14</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.28</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.43</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>3.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.66</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.95</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.98</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.74</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.78</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>8.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.27</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.31</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dt</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11</point></value> and <value><point>6.5</point></value>, <value><point>8</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.44</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				</DIV>
			</DIV>
			<DIV xmlns=""><HEADER>Reprotection of the  <molecule ref="chem13" title="13" xmlns="http://www.xml-cml.org/schema"><name>alcohol</name></molecule></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem13" title="13"><name>alcohol</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">145.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.6</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">3.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="Et3N"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.5</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">3.6</scalar></property></module><module role="container">), DMAP (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">110.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.9</scalar></property></module><module role="container">) and a</module><action title="solution" role="cml:solution"/><module role="container"> of TBSCl (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">106.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.7</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">3.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">15.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water, and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> </module><molecule ref="chem8" title="8"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. Spectral properties of this compound were in agreement with those of the </module><molecule title="cyclopentyl" role="chemical"/><module role="container"> compound </module><molecule ref="chem8" title="8"/><module role="container"> in the above rearrangement.</module></module>
			</DIV>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  compound </module><molecule ref="chem8" title="8"><name>cyclopentyl</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">255.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.72</scalar></property></module><module role="container">) in </module><molecule title="MeOH"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="NaBH4"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">27.2</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.72</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water, and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="afforded" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 5) to</module><action title="yield" role="cml:yield"/><module role="container">the </module><molecule title="alcohol" role="chemical"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. Pr<SP xmlns=""><IT>i</IT></SP><SB xmlns="">2</SB>NEt (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.98</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">5.6</scalar></property></module><module role="container">) and PMBMCl<REF ID="cit11" TYPE="P" xmlns="">11</REF> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">626.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">3.36</scalar></property></module><module role="container">) were added to a</module><action title="solution" role="cml:solution"/><module role="container"> of the above </module><molecule title="alcohol" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">200.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.56</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">2.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">16.0</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="Et2O"/><module role="container">and the organic layer was</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="solution" role="cml:solution"/><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which was purified
by SCC (</module><module role="balancedBrackets"><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 19) to</module><action title="afford" role="cml:give"/><module role="container"> the PMBM </module><molecule title="ether" role="chemical"/><module role="container"> </module><molecule ref="chem14" title="14"/><module role="container"> (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">229.0</scalar></property><module role="container">, 80%; 62% from </module><molecule ref="chem8" title="8"/></module><module role="container">) as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1732</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1612</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>1514</point></value></quantity> (<quantity type="comment">Ph</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.00</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.90</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.06</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.12</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.30</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>2</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.80</point></value></quantity> (<quantity type="integral"><value><point>4</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>2</SB> and 7-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.94</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>9</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.03</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.50</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>-like, <IT>J</IT> <quantity type="coupling"><value><point>4</point></value>, <value><point>6</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.80</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OMe</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.22</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.24</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">8-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.52</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.60</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value></quantity>, <quantity type="comment">C<IT>H</IT><SB>2</SB>Ph</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.71</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.82</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7</point></value></quantity>, <quantity type="comment">-OCH<SB>2</SB>O-</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.87</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>7.25</point></value></quantity> (each <quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>8.5</point></value></quantity>, <quantity type="comment">Ar-H<SB>4</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem14" title="14"><name>3-[(1R,4S)-4-tert-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propyl acetate</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><action title="To a" role="cml:to"/><module role="container">suspension of LAH (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">24.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.64</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="Et2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">dropwise a</module><action title="solution" role="cml:solution"/><module role="container"> of </module><molecule ref="chem14" title="14"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">323.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.64</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="Et2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">15.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">, the </module><property state="cml:excess"/><module role="container"> LAH was decomposed by dropwise addition of </module><molecule title="water" role="chemical"/><module role="container">. The</module><substance title="mixture" role="cml:substance"/><module role="container"> was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">and the</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><module role="container">solvent</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 9) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem15" title="15"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3465</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1613</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>1514</point></value></quantity> (<quantity type="comment">Ph</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.92</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.05</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.13</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.30</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>2</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>,
<peak><quantity type="shift"><value><point>1.78</point></value></quantity> (<quantity type="integral"><value><point>4</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>2</SB> and 7-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.98</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>9</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>3.66</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>5.5</point></value>, <value><point>6</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.77</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">8-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>3.81</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OMe</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.23</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.52</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.68</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value></quantity>, <quantity type="comment">C<IT>H</IT><SB>2</SB>Ph</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.81</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.87</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6.5</point></value></quantity>, <quantity type="comment">-OCH<SB>2</SB>O-</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.89</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>7.27</point></value></quantity> (each <quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>8.5</point></value></quantity>, <quantity type="comment">Ar-H<SB>4</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem15" title="15"><name>3-[(1R,4S)-4-tert-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propan-1-ol</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem15" title="15"><name>alcohol</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">125.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.27</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">a</module><action title="solution" role="cml:solution"/><module role="container"> of IBX<REF ID="cit12" TYPE="P" xmlns="">12</REF> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">188.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.67</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.67</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="water" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">) and the </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">white</scalar></property><module role="container">precipitate was filtered. The filtrate was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 9) to</module><action title="provide" role="cml:provide"/><module role="container">the </module><molecule title="aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem16" title="16"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1721</point></value></quantity> (<quantity type="comment">CHO</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1613</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>1514</point></value></quantity> (<quantity type="comment">Ph</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.93</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.06</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.12</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.23</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>2.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.80</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.92</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value>
and <value><point>8.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.37</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>2.5</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.78</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value>, <value><point>7</point></value> and <value><point>2</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.80</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OMe</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.13</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7</point></value> and <value><point>2.5</point></value>, <value><point>6</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.24</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.42</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.54</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value></quantity>, <quantity type="comment">C<IT>H</IT><SB>2</SB>Ph</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.70</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.76</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7</point></value></quantity>, <quantity type="comment">-OCH<SB>2</SB>O-</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.87</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>7.23</point></value></quantity> (each <quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>8.5</point></value></quantity>, <quantity type="comment">Ar-H<SB>4</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>9.76</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>2</point></value></quantity>, <quantity type="comment">CHO</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem16" title="16"><name>3-[(1R,4S)-4-tert-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propanal</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem17" title="17"><name>vinyl bromide</name><link title="13" to="cit13"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">403.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">1.52</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="Et2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">4.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">Bu<SP xmlns=""><IT>t</IT></SP>Li (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:conc" units="oscUnits:unknown">1.64</scalar></property><module role="container"> in </module><molecule title="pentane" role="chemical"/><module role="container">; </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.93</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">1.52</scalar></property></module><module role="container">) at -</module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">78.0</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at -</module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">78.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">10.0</scalar></property><module role="container">. A</module><action title="solution" role="cml:solution"/><module role="container"> of the </module><molecule title="aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem16" title="16"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">235.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.51</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="Et2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">6.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">to this</module><substance title="mixture" role="cml:substance"/><module role="container"> at -</module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">78.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">. After being quenched with </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NH4Cl"/><module role="container">, the</module><substance title="mixture" role="cml:substance"/><module role="container"> was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> the adduct  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. Then, to a</module><action title="solution" role="cml:solution"/><module role="container"> of the adduct (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">313.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.48</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.5</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">a</module><action title="solution" role="cml:solution"/><module role="container"> of IBX<REF ID="cit12" TYPE="P" xmlns="">12</REF> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">337.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">1.2</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.2</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">16.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="water" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">5.0</scalar></property></module><module role="container">) and the </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">white</scalar></property><module role="container">precipitate was filtered. The filtrate was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 3 : 17) to</module><action title="provide" role="cml:provide"/><module role="container">the </module><property state="cml:conjugated"/><module role="container"> </module><molecule title="ketone" role="chemical"/><module role="container"> </module><molecule ref="chem18" title="18"/><module role="container"> (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">197.0</scalar></property><module role="container">, 63%; 60% from </module><molecule ref="chem16" title="16"/></module><module role="container">) as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1669</point></value></quantity> (<quantity type="comment">conj. C=O</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1613</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>1514</point></value></quantity> (<quantity type="comment">Ph</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak>-<quantity type="shift"><value><point>0.02</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.09</point></value></quantity> (each <quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiMe<SB>2</SB>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.92</point></value></quantity> (each <quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiBu<SP><IT>t</IT></SP>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.96</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.06</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.16</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.18</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.63</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>1</point></value>, <value><point>9</point></value></quantity><quantity type="comment">-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.79</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.92</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>9</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.45</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>2</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.16</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>7</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.79</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>,
<quantity type="peaktype">s</quantity>, <quantity type="comment">OMe</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.26</point></value></quantity> (<quantity type="integral"><value><point>4</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H, 6-H and 11-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.38</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.65</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12</point></value></quantity>, <quantity type="comment">C<IT>H</IT><SB>2</SB>Ph</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.62</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>4.65</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6.5</point></value></quantity>, <quantity type="comment">-OCH<SB>2</SB>O-</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.53</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">tq</quantity>-like, <IT>J</IT> <quantity type="coupling"><value><point>5</point></value> and <value><point>1</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.83</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>7.17</point></value></quantity> (each <quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>9</point></value></quantity>, <quantity type="comment">Ar-H<SB>4</SB></quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem18" title="18"><name>(4E)-6-tert-Butyldimethylsilyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-1-{[(4-methoxyphenyl)methoxy]methoxy}-4-methylhex-4-en-3-one</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem18" title="18"><name>ketone</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">197.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.3</scalar></property></module><module role="container">) dissolved in a</module><substance title="mixture" role="cml:substance"/><module role="container"> of </module><molecule title="CH2Cl2-H2O"/><module role="container"> (18 : 1, </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">6.54</scalar></property><module role="rbracket"/><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">DDQ<REF ID="cit11b" TYPE="P" xmlns="">11<IT>b</IT></REF> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">86.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.36</scalar></property></module><module role="container">). After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">2.0</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><module role="container"> was filtered through </module><molecule title="Celite" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the filtrate</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 9) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem19" title="19"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>228</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3558</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1659</point></value></quantity> (<quantity type="comment">conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.11</point></value></quantity> (each <quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiMe<SB>2</SB>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.87</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.93</point></value></quantity> (each <quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiBu<SP><IT>t</IT></SP>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.98</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.10</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.11</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.29</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>2.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.74</point></value></quantity>
(<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>1</point></value>, <value><point>9</point></value></quantity><quantity type="comment">-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.78</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>9</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.73</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.71</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>2.90</point></value></quantity> (each <quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>-like, <IT>J</IT> <quantity type="coupling"><value><point>3</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.04</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">6-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.25</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.42</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">br d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>6.64</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">td</quantity>-like, <IT>J</IT> <quantity type="coupling"><value><point>5</point></value> and <value><point>1</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem19" title="19"><name>(4E)-6-tert-Butyldimethylsilyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-1-hydroxy-4-methylhex-4-en-3-one</name></molecule></product></productList></reaction></reactionScheme>
			<DIV xmlns=""><HEADER>Oxidation of the  <molecule ref="chem19" title="19" xmlns="http://www.xml-cml.org/schema"><name>[beta]-hydroxy ketone</name></molecule></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem19" title="19"><name>alcohol</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">200.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.4</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">14.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><molecule title="Ac2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">7.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">16.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> with </module><molecule title="water" role="chemical"/><module role="container"> and </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><module role="container">solvent</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 19) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><property state="cml:conjugated"/><module role="container"> </module><molecule title="[beta]-diketone" role="chemical"/><module role="container"> </module><molecule ref="chem20" title="20"/><module role="container">  and the </module><molecule title="acetate" role="chemical"/><module role="container"> </module><molecule ref="chem21" title="21"/><module role="container">  as </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar></property><module role="container"> oils, respectively.</module></module>
				<reactionScheme xmlns="http://www.xml-cml.org/schema"><HEADER xmlns=""> </HEADER><module role="para"><module role="container">[<IT xmlns="">[alpha]</IT>]23D
						-23.4 (<IT xmlns="">c</IT> 0.47, </module><molecule title="CHCl3"/><module role="rbracket"/><module role="container">); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>305</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1583</point></value></quantity> (<quantity type="comment">hydrogen-bonded conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.03</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.09</point></value></quantity> (each <quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiMe<SB>2</SB>
						× 2)</peak>, <peak><quantity type="shift"><value><point>0.81</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.88</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.92</point></value></quantity> (each <quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiBu<SP><IT>t</IT></SP>
						× 2)</peak>, <peak><quantity type="shift"><value><point>1.15</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.30</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.51</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>2.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.69</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.80</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>1</point></value>, <value><point>9</point></value></quantity><quantity type="comment">-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.98</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>7.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.73</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>,
<quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>8</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.38</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.39</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>5.81</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.59</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>16.15</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">enolic OH</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				<reaction role="overallReaction"><productList><product><molecule ref="chem20" title="20"><name>(2E,4E)-6-tert-Butyldimethylsilyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-hydroxy-4-methylhexa-2,4-dienone</name></molecule></product></productList></reaction></reactionScheme>
				<reactionScheme xmlns="http://www.xml-cml.org/schema"><HEADER xmlns=""> </HEADER><module role="para"><module role="container">[<IT xmlns="">[alpha]</IT>]27D
						+10.0 (<IT xmlns="">c</IT> 0.40, </module><molecule title="MeOH"/><module role="rbracket"/><module role="container">); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>231</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1668</point></value></quantity> (<quantity type="comment">conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns=""><IT>[delta]</IT></IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.02</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.11</point></value></quantity> (each <quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiMe<SB>2</SB>
						× 2)</peak>, <peak><quantity type="shift"><value><point>0.85</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.93</point></value></quantity> (each <quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiBu<SP><IT>t</IT></SP>
						× 2)</peak>, <peak><quantity type="shift"><value><point>0.99</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.07</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.13</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.16</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.76</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>1</point></value>, <value><point>9</point></value></quantity><quantity type="comment">-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.78</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>8</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.93</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>9</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.14</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.59</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17.5</point></value> and <value><point>2.5</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>3.07</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17.5</point></value> and <value><point>6.5</point></value>, <value><point>7</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.23</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>,
<quantity type="peaktype">m</quantity>, <quantity type="comment">3-H and 6-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.42</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>6.66</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">td</quantity>-like, <IT>J</IT> <quantity type="coupling"><value><point>5</point></value> and <value><point>1</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				<reaction role="overallReaction"><productList><product><molecule ref="chem21" title="21"><name>(4E)-1-Acetyloxy-6-tert-butyldimethylsilyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-4-methylhex-4-en-3-one</name></molecule></product></productList></reaction></reactionScheme>
			</DIV>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><molecule title="Ac2O"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.5</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">to a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem20" title="20"><name>[beta]-diketone</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">104.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.21</scalar></property></module><module role="container">), </module><molecule title="Et3N"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.04</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.29</scalar></property></module><module role="container">) and DMAP (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">28.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.23</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> </module><molecule title="CH2Cl2"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">, the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">, </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="enol acetate" role="chemical"/><module role="container"> </module><molecule ref="chem22" title="22"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; [<IT xmlns="">[alpha]</IT>]20D
					-10.3 (<IT xmlns="">c</IT> 0.98, </module><molecule title="CHCl3"/></module><module role="container">); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>277</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>1766</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1673</point></value></quantity> (<quantity type="comment">conj. C=O</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1586</point></value></quantity> (<quantity type="comment">conj. C=C</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB>
(<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.07</point></value></quantity> (each <quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiMe<SB>2</SB>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>0.90</point></value></quantity> (each <quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, SiBu<SP><IT>t</IT></SP>
					× 2)</peak>, <peak><quantity type="shift"><value><point>0.82</point></value></quantity></peak>, <peak><quantity type="shift"><value><point>1.16</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.31</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me and 5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.42</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.68</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value> and <value><point>5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.80</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>1</point></value>, <value><point>9</point></value></quantity><quantity type="comment">-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13</point></value> and <value><point>7.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.31</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.78</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.33</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.38</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>5.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>6.20</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">10-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.25</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem22" title="22"><name>(2E,4E)-3-Acetyloxy-6-tert-butyldimethylsilyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-4-methylhexa-2,4-dienone</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">A</module><action title="solution" role="cml:solution"/><module role="container"> of TBAF (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:conc" units="oscUnits:unknown">1.0</scalar></property><module role="container"> in THF; </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.19</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.19</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">to a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem22" title="22"><name>acetate</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">104.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.19</scalar></property></module><module role="container">) in </module><property state="cml:dry"/><module role="container"> THF (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">4.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="Et2O-hexane" role="chemical"/><module role="container">, 1 : 4 [~~] </module><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="alcohol" role="chemical"/><module role="container"> </module><molecule ref="chem23" title="23"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">colorless</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; [<IT xmlns="">[alpha]</IT>]24D
					+0.98 (<IT xmlns="">c</IT> 1.02, </module><molecule title="CHCl3"/></module><module role="container">); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>277</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3604</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3508</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1767</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1674</point></value></quantity> (<quantity type="comment">conj. C=O</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1587</point></value></quantity> (<quantity type="comment">conj. C=C</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.01</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiMe<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.86</point></value></quantity> (<quantity type="integral"><value><point>9</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">SiBu<SP><IT>t</IT></SP></quantity>)</peak>, <peak><quantity type="shift"><value><point>0.82</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>1.16</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment"><IT>gem</IT>-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.31</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>,
<quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.42</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.68</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.85</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.87</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.31</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.78</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.33</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.38</point></value></quantity> (<quantity type="integral"><value><point>2</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>6</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H<SB>2</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>6.25</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">10-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.28</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem23" title="23"><name>(2E,4E)-3-Acetyloxy-1-[(1R,4S)-4-tert-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-6-hydroxy-4-methylhexa-2,4-dienone</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">To a</module><action title="solution" role="cml:solution"/><module role="container"> of the  </module><molecule ref="chem23" title="23"><name>alcohol</name></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">54.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.13</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.25</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">a</module><action title="solution" role="cml:solution"/><module role="container"> of IBX<REF ID="cit12" TYPE="P" xmlns="">12</REF> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">72.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.26</scalar></property></module><module role="container">) in </module><molecule title="DMSO" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.26</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">and the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">. The reaction</module><substance title="mixture" role="cml:substance"/><action title="was diluted" role="cml:diluted"/><module role="container">with </module><molecule title="water" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">3.0</scalar></property></module><module role="container">) and the </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">white</scalar></property><module role="container">precipitate was filtered. The filtrate was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="acetone-hexane" role="chemical"/><module role="container">, 3 : 17) to</module><action title="afford" role="cml:give"/><module role="container"> the </module><molecule title="aldehyde" role="chemical"/><module role="container">  as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">pale</scalar><scalar dictRef="osc:colour" dataType="xsd:string">yellow</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">. A</module><substance title="mixture" role="cml:substance"/><module role="container"> of 47% </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="HF-CH3CN"/><module role="container"> (1 : 19; </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.4</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">to a</module><action title="solution" role="cml:solution"/><module role="container"> of this </module><molecule title="aldehyde" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">33.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.08</scalar></property></module><module role="container">) in a</module><substance title="mixture" role="cml:substance"/><module role="container"> of CH<SB xmlns="">3</SB>CN-THF (9 : 1; </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">4.0</scalar></property><module role="rbracket"/><module role="container">) at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.5</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><module role="container"> was quenched with </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container">and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. Standard work-up</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="balancedBrackets"><molecule title="acetone-hexane" role="chemical"/><module role="container">, 3 :
7) to</module><action title="provide" role="cml:provide"/><module role="container">the desilylated </module><molecule title="aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem10b" title="10b"/><module role="container"> (</module><module role="lbracket"/><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">22.0</scalar></property><module role="container">, 92%; 55% from </module><molecule ref="chem23" title="23"/></module><module role="container">) as a </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">pale</scalar><scalar dictRef="osc:colour" dataType="xsd:string">yellow</scalar><scalar dictRef="osc:nonsolidstate" dataType="xsd:string">oil</scalar></property><module role="container">; [<IT xmlns="">[alpha]</IT>]26D
					-10.0 (<IT xmlns="">c</IT> 0.40, </module><molecule title="CHCl3"/><module role="rbracket"/><module role="container">); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>283</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3611</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3476</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1773</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1674</point></value></quantity> (<quantity type="comment">conj. C=O and conj. CHO</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1588</point></value></quantity> (<quantity type="comment">conj. C=C</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.84</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.19</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.35</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.46</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>3</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.70</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.96</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.31</point></value></quantity></peak> and <peak><quantity type="shift"><value><point>2.33</point></value></quantity> (each <quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me and OAc</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.85</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>8.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.47</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.37</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>7.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.60</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>10.17</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT>
<quantity type="coupling"><value><point>7.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem10b" title="10b"><name>(2E,4E)-4-Acetyloxy-6-[(1R,4S)-4-hydroxy-1,2,2-trimethylcyclopentyl]-3-methyl-6-oxohexa-2,4-dienal</name></molecule></product></productList></reaction></reactionScheme>
			<reactionScheme><HEADER xmlns=""> </HEADER>
				<module role="para"><module role="container">An </module><property state="cml:acidic"/><action title="solution" role="cml:solution"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.1</scalar></property></module><module role="container">) prepared from PTSA (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">500.0</scalar></property></module><module role="container">) and </module><molecule title="H3PO4"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">725.0</scalar></property></module><module role="container">) in </module><molecule title="MeOH"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">37.5</scalar></property></module><module role="container">) and  (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">0.1</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.91</scalar></property></module><module role="container">) were added to a</module><action title="solution" role="cml:solution"/><module role="container"> of the Wittig salt </module><molecule ref="chem24" title="24"><name>trimethyl orthoformate</name><link title="14" to="cit14"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">35.6</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.08</scalar></property></module><module role="container">) in </module><molecule title="MeOH"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">). The</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dictRef="osc:temperature" dataType="xsd:double" units="oscUnits:k">298.15</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container"> and neutralized with </module><molecule title="NaOMe"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:conc" units="oscUnits:unknown">1.0</scalar></property><module role="container"> in </module><molecule title="MeOH"/></module><module role="container">) until just before the </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">red</scalar></property><module role="container"> color of an </module><module role="container">appeared.</module><action title="Evaporation" role="cml:evaporation"/><module role="container">of the solvent</module><action title="provided" role="cml:provide"/><module role="container"> the Wittig salt </module><molecule ref="chem25" title="25"><name>ylide</name></molecule><module role="container">, to which a</module><action title="solution" role="cml:solution"/><module role="container"> of the </module><molecule title="aldehyde" role="chemical"/><module role="container"> </module><molecule ref="chem10b" title="10b"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">9.8</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.03</scalar></property></module><module role="container">) in </module><molecule title="propan-2-ol" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.5</scalar></property></module><module role="container">) was added. To the</module><substance title="mixture" role="cml:substance"/><module role="container">, a </module><property state="cml:basic"/><action title="solution" role="cml:solution"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">) of </module><molecule title="KOH"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">500.0</scalar></property></module><module role="container">) dissolved in </module><molecule title="water" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">) and </module><molecule title="propan-2-ol" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">10.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">dropwise at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:h">1.0</scalar></property><module role="container">, the</module><substance title="mixture" role="cml:substance"/><module role="container">was</module><action title="poured" role="cml:poured"/><module role="container"> into ice-water, and</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">. The</module><action title="extract" role="cml:extract"/><module role="container">s were shaken with </module><property state="cml:aqueous"/><module role="container"> 5% </module><molecule title="HCl"/><module role="container">
until the fine structure disappeared on UV-VIS,</module><action title="washed" role="cml:washed"/><module role="container"> successively with </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NaHCO3"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="provided" role="cml:provide"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="acetone-hexane" role="chemical"/><module role="container">, 1 : 4) to</module><action title="afford" role="cml:give"/><module role="container"> an isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> of </module><molecule title="apocarotenal" role="chemical"/><module role="container"> </module><molecule ref="chem26" title="26"/><module role="container">  in which the main product was all-<IT xmlns="">E</IT>isomer. Purification of a part of the isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> by PTLC (</module><module role="lbracket"/><molecule title="acetone-hexane" role="chemical"/><module role="container">, 3 : 7)</module><action title="provided" role="cml:provide"/><module role="container"> the all-<IT xmlns="">E</IT> isomer as an </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">orange</scalar><scalar dictRef="osc:solidstate" dataType="xsd:string">solid</scalar></property><module role="container">; <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>419</point></value></quantity></peak> and <peak><quantity type="lmax"><value><point>440</point></value></quantity>(<quantity type="peaktype">sh</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3610</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3476</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1665</point></value></quantity> (<quantity type="comment">conj. CHO</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1605</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>1568</point></value></quantity> (<quantity type="comment">conj. C=C or hydrogen-bonded conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.85</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.19</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.35</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.55</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>3</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.72</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[beta]</SB></quantity>)</peak>,
<peak><quantity type="shift"><value><point>1.90</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.00</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.06</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.09</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>8.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.53</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>5.87</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.41</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.65</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value>, <value><point>12</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.74</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.77</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>11.5</point></value>, <value><point>15</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.97</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>7.03</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>11.5</point></value>, <value><point>15</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>7.23</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>9.48</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">12'-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
			<reaction role="overallReaction"><productList><product><molecule ref="chem26" title="26"><name>(2E,4E,6E,8E,10E,12E)-12-Hydroxy-14-[(1R,4S)-4-hydroxy-1,2,2-trimethylcyclopentyl]-2,7,11-trimethyl-14-oxotetradeca-2,4,6,8,10,12-hexaenal</name></molecule></product></productList></reaction></reactionScheme>
			<DIV xmlns=""><HEADER>Synthesis of <molecule title="mytiloxanthin" role="chemical" xmlns="http://www.xml-cml.org/schema"/></HEADER>
				<module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container">A </module><property state="cml:basic"/><action title="solution" role="cml:solution"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">3.0</scalar></property></module><module role="container">) of </module><molecule title="KOH"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">500.0</scalar></property></module><module role="container">) dissolved in </module><molecule title="water" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">1.0</scalar></property></module><module role="container">) and </module><molecule title="propan-2-ol" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">10.0</scalar></property></module><module role="container">)</module><action title="was added" role="cml:added"/><module role="container">dropwise to a</module><action title="solution" role="cml:solution"/><module role="container"> of the </module><molecule title="apocarotenal" role="chemical"/><module role="container"> </module><molecule ref="chem26" title="26"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">11.7</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.03</scalar></property></module><module role="container">) and the Wittig salt </module><molecule ref="chem27" title="27"><link title="15" to="cit15"/></molecule><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:mass" units="oscUnits:mg">61.0</scalar><scalar dataType="xsd:double" dictRef="osc:amount" units="oscUnits:mmol">0.12</scalar></property></module><module role="container">) in </module><molecule title="propan-2-ol" role="chemical"/><module role="container"> (</module><module role="balancedBrackets"><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:volume" units="oscUnits:mL">6.0</scalar></property></module><module role="container">) at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container">. After being</module><action title="stirred" role="cml:stirred"/><module role="container"> at </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:temperature" units="oscUnits:C">0.0</scalar></property><module role="container"> for </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:time" units="oscUnits:min">30.0</scalar></property><module role="container">, the reaction</module><substance title="mixture" role="cml:substance"/><module role="container"> was</module><action title="extract" role="cml:extract"/><module role="container">ed with </module><molecule title="Et2O"/><module role="container">and</module><action title="washed" role="cml:washed"/><module role="container"> with </module><property state="cml:saturated"/><module role="container"> </module><property state="cml:aqueous"/><module role="container"> </module><molecule title="NH4Cl"/><module role="container"> and </module><molecule title="brine" role="chemical"/><module role="container">.</module><action title="Evaporation" role="cml:evaporation"/><module role="container"> of the </module><property state="cml:dry"/><action title="extract" role="cml:extract"/><module role="container">s</module><action title="gave" role="cml:give"/><module role="container">a</module><substance title="residue" role="cml:substance"/><module role="container">, which</module><action title="was purified by" role="cml:purified"/><module role="container">SCC (</module><module role="lbracket"/><molecule title="acetone-hexane" role="chemical"/><module role="container">, 3 : 7) to</module><action title="afford" role="cml:give"/><module role="container"> an isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> of </module><molecule title="mytiloxanthin" role="chemical"/><module role="container"> . Purification of a part of the isomeric</module><substance title="mixture" role="cml:substance"/><module role="container"> by PHPLC [CHEMCOSORB 7ODS-H 1.0 × 30 cm; </module><molecule title="H2O-MeOH"/><module role="container">, 4 : 96; </module><property dictRef="osc:quantity"><scalar dataType="xsd:double" dictRef="osc:conc" units="oscUnits:unknown">460.0</scalar></property><module role="container">detect.]</module><action title="provided" role="cml:provide"/><module role="container"> the all-<IT xmlns="">E</IT> isomer </module><molecule ref="chem1" title="1"/><module role="container">, 9<IT xmlns="">Z</IT> one </module><molecule ref="chem28" title="28"/><module role="container"> and
9<IT xmlns="">Z</IT>,11<IT xmlns="">Z</IT> one </module><molecule ref="chem29" title="29"/><module role="container"> as </module><property dictRef="osc:nature"><scalar dictRef="osc:colour" dataType="xsd:string">red</scalar></property><module role="container"> solids respectively, in a </module><property state="cml:pure"/><module role="container"> state. Spectral properties of the synthetic all-<IT xmlns="">E</IT> isomer </module><molecule ref="chem1" title="1"/><module role="container"> and 9<IT xmlns="">Z</IT> one </module><molecule ref="chem28" title="28"><link title="4" to="cit4"/></molecule><module role="container"> were in agreement with those of a natural specimen.</module></module>
				<DIV><HEADER>all-<IT>E</IT> Isomer <molecule ref="chem1" title="1" xmlns="http://www.xml-cml.org/schema"/></HEADER><module role="para" xmlns="http://www.xml-cml.org/schema"><molecule title="CD ()/nm" role="chemical"/><module role="container"> ([Delta]<IT xmlns="">[epsilon]</IT>) 230 (-0.5), 275 (0), 294 (+0.7), 310 (0), 360 (-0.3); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>470</point></value></quantity></peak></peaks></spectrum><module role="container">, <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>(<quantity type="solvent" xmlns="">Et<SB>2</SB>O</quantity>)/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>467</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3530</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3321</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1602</point></value></quantity> (<quantity type="comment">hydrogen-bonded conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.85</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1'-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.14</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.19</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1'-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.20</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.35</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.45</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.55</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.71</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.83</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.92</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.98</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13-Me and 13'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.99</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.01</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.07</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.09</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT>
<quantity type="coupling"><value><point>13.5</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.43</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">br dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>18</point></value> and <value><point>5.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>9</point></value>, <value><point>4</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.00</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.52</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>5.86</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.28</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.36</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value>, <value><point>12</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.38</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.46</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.55</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>11.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.60</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.64</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>11</point></value>, <value><point>15</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.65</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15.5</point></value>, <value><point>12</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.71</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>11.5</point></value>, <value><point>15</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>7.23</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">'-H</quantity>)</peak></peaks></spectrum><module role="container"> .</module></module>
				</DIV>
				<DIV><HEADER>9<IT>Z</IT>-Isomer <molecule ref="chem28" title="28" xmlns="http://www.xml-cml.org/schema"/></HEADER><module role="para" xmlns="http://www.xml-cml.org/schema"><molecule title="CD ()/nm" role="chemical"/><module role="container"> ([Delta]<IT xmlns="">[epsilon]</IT>) 230 (-0.8), 247 (0), 258 (+1.0), 280 (0), 300 (-0.3), 310 (0), 350 (+1.0), 370 (0); <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>467</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>358</point></value></quantity></peak></peaks></spectrum><module role="container"> <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>(<quantity type="solvent" xmlns="">Et<SB>2</SB>O</quantity>)/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>465</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>358</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3530</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3321</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1602</point></value></quantity> (<quantity type="comment">hydrogen-bonded conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.85</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1'-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.19</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>ax</SB> and 1'-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.26</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.35</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.48</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.56</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.72</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>4.5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.93</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">ddd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>3</point></value> and <value><point>2</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.95</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.97</point></value></quantity> (<quantity type="integral"><value><point>6</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me and 9'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.99</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.01</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>,
<quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.09</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.10</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.46</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">br dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17.5</point></value> and <value><point>4.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.88</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>9</point></value>, <value><point>4</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>4.01</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.53</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>5.86</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.27</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11</point></value>, <value><point>14</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.30</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>11.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.35</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15.5</point></value>, <value><point>12</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.37</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.63</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15.5</point></value> and <value><point>12</point></value>, <value><point>15</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.64</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.65</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value>, <value><point>12</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.71</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>11</point></value>, <value><point>15</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.87</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>11</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>7.23</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">'-H</quantity>)</peak></peaks></spectrum><module role="container"> (the cross peak was observed between 11-H and 5-Me in the NOESY spectrum) .</module></module>
				</DIV>
				<DIV><HEADER>9<IT>Z</IT>,11<IT>Z</IT>-Isomer <molecule ref="chem29" title="29" xmlns="http://www.xml-cml.org/schema"/></HEADER><module role="para" xmlns="http://www.xml-cml.org/schema"><module role="container"><IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>463</point></value></quantity></peak> and <peak><quantity type="lmax"><value><point>296</point></value></quantity></peak></peaks></spectrum><module role="container">, <IT xmlns="">[lambda]</IT></module><spectrum type="uv"><SB xmlns="">max</SB>(<quantity type="solvent" xmlns="">Et<SB>2</SB>O</quantity>)/nm <peaks type=".." xmlns=""><peak><quantity type="lmax"><value><point>460</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>447</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>294</point></value></quantity></peak></peaks></spectrum><module role="container">; <IT xmlns="">[nu]</IT></module><spectrum type="ir"><SB xmlns="">max</SB>/cm<SP xmlns="">-1</SP> <peaks type=".." xmlns=""><peak><quantity type="vmax"><value><point>3530</point></value></quantity></peak> and <peak><quantity type="vmax"><value><point>3321</point></value></quantity> (<quantity type="comment">OH</quantity>)</peak>, <peak><quantity type="vmax"><value><point>1602</point></value></quantity> (<quantity type="comment">hydrogen-bonded conj. C=O</quantity>)</peak></peaks></spectrum><module role="container">; <IT xmlns="">[delta]</IT></module><spectrum type="hnmr"><SB xmlns="">H</SB> (<quantity type="frequency" xmlns=""><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".." xmlns=""><peak><quantity type="shift"><value><point>0.83</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1'-Me<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.15</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.17</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1'-Me<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.21</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">1-Me<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.33</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.45</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12</point></value>, <value><point>2</point></value></quantity><quantity type="comment">-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.56</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.70</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14</point></value> and <value><point>5</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[beta]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.83</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">2-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>1.93</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">5-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.96</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>1.97</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13'-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.01</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">9-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.05</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">4-H<SB>ax</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.07</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>13.5</point></value> and <value><point>8</point></value>, <value><point>2</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.08</point></value></quantity> (<quantity type="integral"><value><point>3</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">13-Me</quantity>)</peak>, <peak><quantity type="shift"><value><point>2.43</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">br dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>17</point></value> and <value><point>5.5</point></value>,
<value><point>4</point></value></quantity><quantity type="comment">-H<SB>eq</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>2.86</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>14.5</point></value> and <value><point>8.5</point></value>, <value><point>4</point></value></quantity><quantity type="comment">'-H<SB>[alpha]</SB></quantity>)</peak>, <peak><quantity type="shift"><value><point>3.99</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>4.51</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">m</quantity>, <quantity type="comment">3'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>5.84</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">s</quantity>, <quantity type="comment">7'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>5.95</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12.5</point></value>, <value><point>12</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.27</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10</point></value>, <value><point>14</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.36</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>14</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.50</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">t</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.58</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>11</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.61</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>15</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.63</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value>, <value><point>12</point></value></quantity><quantity type="comment">'-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.66</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">dd</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>15</point></value> and <value><point>10.5</point></value>, <value><point>15</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>6.78</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>12.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">-H</quantity>)</peak>, <peak><quantity type="shift"><value><point>7.21</point></value></quantity> (<quantity type="integral"><value><point>1</point></value><units>H</units></quantity>, <quantity type="peaktype">d</quantity>, <IT>J</IT> <quantity type="coupling"><value><point>10.5</point></value>, <value><point>10</point></value></quantity><quantity type="comment">'-H</quantity>)</peak></peaks></spectrum><module role="container"> (the cross peak was observed between 11-H and 12-H in the NOESY spectrum) .</module></module>
				</DIV>
			</DIV>
		</module>
	</module><ACKNOWLEDGMENTS xmlns="">We thank Dr T. Maoka, Kyoto Pharmaceutical University for his kind gift of spectral data on natural mytiloxanthins. We are also grateful for the chemical support from Drs U. Hengartner and K. Bernherd, Hoffmann-La Roche Ltd., Basel, Switzerland.</ACKNOWLEDGMENTS>
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		<FOOTNOTELIST xmlns=""><FOOTNOTE ID="fn1" MARKER="1">We have employed the numbering system used in carotenoids.</FOOTNOTE></FOOTNOTELIST><FIGURELIST xmlns=""><FIGURE SEQ="scheme" SRC="scheme1" ID="sch1"><TITLE/></FIGURE><FIGURE SEQ="scheme" SRC="scheme2" ID="sch2"><TITLE/></FIGURE><FIGURE SEQ="scheme" SRC="scheme3" ID="sch3"><TITLE><IT>Reagents and conditions</IT>: a, <formula><chemical SMILES="CC(=O)OC(=O)O" InChI="InChI=1/C3H4O4/c1-2(4)7-3(5)6/h1H3,(H,5,6)">Ac<SB>2</SB>O</chemical></formula>, Py; b, MCPBA; c, <formula><chemical>TMSCl</chemical></formula>, <formula><chemical SMILES="[Na+].[I-]" InChI="InChI=1/HI.Na/h1H;/q;+1/p-1">NaI</chemical></formula>; d, TBSCl, <formula><chemical SMILES="CCN(CC)CC" InChI="InChI=1/C6H15N/c1-4-7(5-2)6-3/h4-6H2,1-3H3">Et<SB>3</SB>N</chemical></formula>, DMAP; e, <XREF ID="chem9" TYPE="COMPOUND">9</XREF>; f, <formula><chemical SMILES="[Na+].[BH4-]" InChI="InChI=1/BH4.Na/h1H4;/q-1;+1">NaBH<SB>4</SB></chemical></formula>; g, PMBMCl, Pr<SP><IT>i</IT></SP><SB>2</SB>NEt; <chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical>, LAH; i, IBX; j; <XREF ID="chem17" TYPE="COMPOUND">17</XREF>, Bu<SP><IT>t</IT></SP>Li; k, DDQ; l, <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical>, <formula><chemical SMILES="CC(=O)OC(=O)O" InChI="InChI=1/C3H4O4/c1-2(4)7-3(5)6/h1H3,(H,5,6)">Ac<SB>2</SB>O</chemical></formula>.</TITLE></FIGURE><FIGURE SEQ="scheme" SRC="scheme4" ID="sch4"><TITLE><IT>Reagents and conditions</IT>: a, <formula><chemical SMILES="CC(=O)OC(=O)O" InChI="InChI=1/C3H4O4/c1-2(4)7-3(5)6/h1H3,(H,5,6)">Ac<SB>2</SB>O</chemical></formula>, <formula><chemical SMILES="CCN(CC)CC" InChI="InChI=1/C6H15N/c1-4-7(5-2)6-3/h4-6H2,1-3H3">Et<SB>3</SB>N</chemical></formula>, DMAP; b, TBAF; c, IBX; d, <formula><chemical SMILES="[H]F" InChI="InChI=1/FH/h1H">HF</chemical></formula>; e; <chemical><formula>HC</formula>(<formula>OMe</formula>)<SB>3</SB></chemical>, <chemical SMILES="[O-]C1=CC=CC=C1([O-])" InChI="InChI=1/C6H6O2/c7-5-3-1-2-4-6(5)8/h1-4,7-8H/p-2">cat</chemical>. <chemical SMILES="[H+]" InChI="InChI=1/p+1/fH/q+1">H<SP>+</SP></chemical> then 1 M <formula><chemical>NaOMe</chemical></formula>; f, <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> then <chemical SMILES="[H+]" InChI="InChI=1/p+1/fH/q+1">H<SP>+</SP></chemical>; g, <XREF ID="chem27" TYPE="COMPOUND">27</XREF>, <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula>.</TITLE></FIGURE></FIGURELIST><TABLELIST xmlns=""/><cmlPile xmlns=""><cml id="InChI=1/C2H4O/c1-2-3-1/h1-2H2" xmlns="http://www.xml-cml.org/schema/cml2/core"><molecule id="m1"><atomArray><atom id="a1" elementType="O"><label value="1"/></atom><atom id="a2" elementType="C"><label value="2"/></atom><atom id="a3" elementType="C"><label value="3"/></atom></atomArray><bondArray><bond atomRefs2="a1 a2" order="1"/><bond atomRefs2="a2 a3" order="1"/><bond atomRefs2="a3 a1" order="1"/></bondArray></molecule></cml><cml id="InChI=1/C2H3.Li/c1-2;/h1H,2H2;/q;+1" xmlns="http://www.xml-cml.org/schema/cml2/core"><molecule id="m1"><atomArray><atom id="a1" elementType="Li" formalCharge="1"><label value="1"/></atom><atom id="a2" elementType="C"><label value="1"/></atom><atom id="a3" elementType="C"><label value="2"/></atom></atomArray><bondArray><bond atomRefs2="a2 a3" order="2"/><bond atomRefs2="a2 a1" order="1"/></bondArray></molecule></cml><cml id="InChI=1/C2H3Br/c1-2-3/h2H,1H2" xmlns="http://www.xml-cml.org/schema/cml2/core"><molecule id="m1"><atomArray><atom id="a1" elementType="C"><label value="1"/></atom><atom id="a2" elementType="C"><label value="2"/></atom><atom id="a3" elementType="Br"><label value="1"/></atom></atomArray><bondArray><bond atomRefs2="a1 a2" order="2"/><bond atomRefs2="a3 a1" order="1"/></bondArray></molecule></cml><cml id="InChI=1/C2H6O/c1-2-3/h3H,2H2,1H3" xmlns="http://www.xml-cml.org/schema/cml2/core"><molecule id="m1"><atomArray><atom id="a1" elementType="C"><label value="1"/></atom><atom id="a2" elementType="C"><label value="2"/></atom><atom id="a3" elementType="O"/></atomArray><bondArray><bond atomRefs2="a1 a2" order="1"/><bond atomRefs2="a3 a1" order="1"/></bondArray></molecule></cml></cmlPile></cml>
