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<PAPER><METADATA><FILENO>b201228f</FILENO><PAPERTYPE>article</PAPERTYPE><JOURNAL><NAME>P1</NAME><YEAR>2002</YEAR><VOLUME/><ISSUE>13</ISSUE><PAGES>1581-1587</PAGES></JOURNAL></METADATA><TITLE>Carotenoids and related <chemical>polyenes</chemical>. Part 8.<REF ID="cit1" TYPE="P">1</REF> Total synthesis of optically active <chemical>mytiloxanthin</chemical> applying the stereoselective rearrangement of tetrasubstituted <chemical>epoxide</chemical><XREF ID="fn1" TYPE="FOOTNOTE_MARKER"/></TITLE><AUTHORLIST><AUTHOR ID="1"><NAME>Chisato<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR ID="2"><NAME>Yumiko<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR ID="3"><NAME>Masayoshi<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><ABSTRACT>Biomimetic synthesis of <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF> was accomplished with stereoselective rearrangement of the tetrasubstituted <chemical>epoxide</chemical> <XREF ID="chem5" TYPE="COMPOUND">5</XREF> as a key reaction. This is the first total synthesis of optically active all-<IT>E</IT> <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF>.</ABSTRACT><BODY>
		<DIV><HEADER>Introduction</HEADER>
			<P><chemical>Mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF>, with a unique <chemical>cyclopentyl enolic β-diketone</chemical> group conjugated to a <chemical>polyene</chemical> chain, was first isolated from <IT>Mytilus californianus</IT> by Scheer in 1940.<REF ID="cit2" TYPE="P">2</REF> Its structure and synthesis of the 9<IT>Z</IT>-isomer were reported by Weedon's group,<REF ID="cit3" TYPE="P">3</REF> they developed the new synthetic route to <chemical>polyene β-diketones</chemical> using Claisen type condensation between <chemical>polyene</chemical> esters and <chemical>methyl ketones</chemical>. The absolute configuration was determined by Maoka and Fujiwara in 1996.<REF ID="cit4" TYPE="P">4</REF> The <chemical>cyclopentyl</chemical> end group of <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF> is believed<REF ID="cit3" TYPE="P">3</REF> to be formed in Nature from the <chemical>epoxide</chemical> end group of <chemical>5,6-epoxy</chemical> carotenoids such as <chemical>halocynthiaxanthin</chemical> <XREF ID="chem2" TYPE="COMPOUND">2</XREF> by cleavage of the <chemical SMILES="O1CC1" InChI="InChI=1/C2H4O/c1-2-3-1/h1-2H2" liveInChI="yes">oxirane</chemical> ring at the C-5 position and successive ring contraction (a <chemical>pinacolic</chemical> rearrangement)
(Scheme 1, route <IT>a</IT>).</P>
			
			<P>We found<REF ID="cit5" TYPE="P">5</REF> that the acyclic-tetrasubstituted olefinic compounds and the <chemical>cyclopentyl ketone</chemical> were derived by Lewis acid-promoted stereoselective rearrangement of <chemical>epoxy</chemical> compounds. Then, the biomimetic total synthesis<REF ID="cit1 cit6" TYPE="P">1,6</REF> of <chemical>crassostreaxanthin</chemical> B <XREF ID="chem3" TYPE="COMPOUND">3</XREF> possessing the acyclic-tetrasubstituted olefinic end group was achieved using this rearrangement reaction.</P>
			<P>In a previous communication,<REF ID="cit7" TYPE="P">7</REF> we reported the first total synthesis of <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF> which includes the new construction of conjugated <chemical>β-diketones</chemical> <XREF ID="chem10a chem10b" TYPE="COMPOUND">10a,b</XREF> through the <chemical>cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF> (Scheme 2), prepared by application of the stereoselective rearrangement of <chemical>epoxide</chemical> <XREF ID="chem5" TYPE="COMPOUND">5</XREF>. The present paper is concerned with a full account of the experiments.</P>
			
		</DIV>
		<DIV><HEADER>Results and discussion</HEADER>
			<P>It has been previously reported<REF ID="cit5b" TYPE="P">5<IT>b</IT></REF> that <chemical><formula>BF<SB>3</SB><B>·</B></formula>OEt<SB>2</SB>-treatment</chemical> of the <chemical>epoxide</chemical> <XREF ID="chem4" TYPE="COMPOUND">4</XREF> (Scheme 2) with the <chemical>acetoxy ethyl</chemical> group at the C-6 position resulted in a very slow reaction and in a low-yield formation of the C-5 diastereomer <XREF ID="chem6" TYPE="COMPOUND">6</XREF> instead of the desired compound <XREF ID="chem7" TYPE="COMPOUND">7</XREF>. Efficient preparation of <XREF ID="chem7" TYPE="COMPOUND">7</XREF> was obtained from the investigation of other Lewis acids with an <chemical>aminium</chemical> salt. Thus, treatment of the <chemical>epoxide</chemical> <XREF ID="chem4" TYPE="COMPOUND">4</XREF> with <chemical>tris(4-bromophenyl)aminium hexachloroantimonate</chemical> <XREF ID="chem9" TYPE="COMPOUND">9</XREF><REF ID="cit8" TYPE="P">8</REF> in <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> was found to afford <XREF ID="chem7" TYPE="COMPOUND">7</XREF> in reasonable yield (69%) (Scheme
2). In order to accomplish the biomimetic synthesis of <XREF ID="chem1" TYPE="COMPOUND">1</XREF> in an analogous manner to the successful synthesis of <XREF ID="chem3" TYPE="COMPOUND">3</XREF>, the <chemical>acetoxy</chemical> group at the C-3 position in <XREF ID="chem4" TYPE="COMPOUND">4</XREF> was replaced by the <chemical><IT>tert</IT>-butyldimethylsilyl</chemical> (TBS) <chemical>ether</chemical> leading to <chemical>epoxide</chemical> <XREF ID="chem5" TYPE="COMPOUND">5</XREF>. The synthetic route of <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF> was therefore planned through conversion of <XREF ID="chem5" TYPE="COMPOUND">5</XREF> to the <chemical>cyclopentyl ketone</chemical> <XREF ID="chem8" TYPE="COMPOUND">8</XREF> and subsequent construction of <chemical>enolic β-diketone</chemical> as shown in Scheme 2.</P>
			<P>Starting from the previously prepared optically active <chemical>alcohol</chemical><REF ID="cit1" TYPE="P">1</REF>
				<XREF ID="chem11" TYPE="COMPOUND">11</XREF> (Scheme 3), acetylation followed by epoxidation with MCPBA gave <chemical>epoxides</chemical> <XREF ID="chem5a chem5b" TYPE="COMPOUND">5a,b</XREF> (<XREF ID="chem5a" TYPE="COMPOUND">5a</XREF>: 26% from <XREF ID="chem11" TYPE="COMPOUND">11</XREF>; <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF>: 48% from <XREF ID="chem11" TYPE="COMPOUND">11</XREF>), in which the relative configurations between the <chemical>silyloxy</chemical> and <chemical>epoxy</chemical> groups were confirmed by <SP>1</SP>H NMR.<REF ID="cit9" TYPE="P">9</REF> The undesired isomer <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF> was returned to the tetrasubstituted <chemical>olefin</chemical> <XREF ID="chem12" TYPE="COMPOUND">12</XREF> by the following deepoxidation procedure. Treatment of <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF> with <formula><chemical>TMSCl</chemical></formula> and <formula><chemical SMILES="[Na+].[I-]" InChI="InChI=1/HI.Na/h1H;/q;+1/p-1">NaI</chemical></formula> in dry <chemical SMILES="CC#N" InChI="InChI=1/C2H3N/c1-2-3/h1H3">acetonitrile</chemical><REF ID="cit10" TYPE="P">10</REF>
followed by silylation gave <XREF ID="chem12" TYPE="COMPOUND">12</XREF> in 60% yield. Reaction of <chemical><IT>anti</IT>-epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> with <chemical>aminium</chemical> salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF> provided the desired <chemical>cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF> (63%) and its deprotected <chemical>alcohol</chemical> <XREF ID="chem13" TYPE="COMPOUND">13</XREF> (30%) which was easily resilylated to give <XREF ID="chem8" TYPE="COMPOUND">8</XREF> (89%). Consequently, the <chemical>cyclopentyl ketone</chemical> <XREF ID="chem8" TYPE="COMPOUND">8</XREF> was synthesized by the stereoselective rearrangement of <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> in high yield. The structure of <XREF ID="chem8" TYPE="COMPOUND">8</XREF> was determined from the following spectral data. Its IR absorption showed a new <chemical>carbonyl</chemical> frequency at 1699 cm<SP>–1</SP>. In its <SP>1</SP>H NMR spectrum, the <chemical>methylene</chemical> signal of the C-7 position appeared at <IT>δ</IT>
2.75 (t), further downfield than the corresponding signal [<IT>δ</IT> 2.01 (2H, m)] of <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF>, in addition, <chemical SMILES="[H+]" InChI="InChI=1/p+1/i/hH">proton</chemical> signals on the <chemical SMILES="C1CCCC1" InChI="InChI=1/C5H10/c1-2-4-5-3-1/h1-5H2">cyclopentane</chemical> ring were observed analogous to results reported previously.<REF ID="cit5b" TYPE="P">5<IT>b</IT></REF></P>
			
			<P>Reduction of <XREF ID="chem8" TYPE="COMPOUND">8</XREF> with <formula><chemical SMILES="[Na+].[BH4-]" InChI="InChI=1/BH4.Na/h1H4;/q-1;+1">NaBH<SB>4</SB></chemical></formula> followed by protection of the resulting <chemical>hydroxy</chemical> group with <chemical><IT>p</IT>-methoxybenzyloxymethyl</chemical> (PMBM) <chemical SMILES="[Cl-]" InChI="InChI=1/ClH/h1H/p-1/fCl/h1h/q-1">chloride</chemical><REF ID="cit11" TYPE="P">11</REF> gave compound <XREF ID="chem14" TYPE="COMPOUND">14</XREF> (62% from <XREF ID="chem8" TYPE="COMPOUND">8</XREF>), which was reduced with LAH to provide the <chemical>alcohol</chemical> <XREF ID="chem15" TYPE="COMPOUND">15</XREF> (99%). This was subjected to oxidation with <chemical><IT>o</IT>-iodoxybenzoic acid</chemical><REF ID="cit12" TYPE="P">12</REF> (IBX) to yield the <chemical>aldehyde</chemical> <XREF ID="chem16" TYPE="COMPOUND">16</XREF> (93%), which was reacted with <chemical SMILES="[Li+]C=C" InChI="InChI=1/C2H3.Li/c1-2;/h1H,2H2;/q;+1" liveInChI="yes">vinyllithium</chemical> prepared from the <chemical SMILES="C=CBr" InChI="InChI=1/C2H3Br/c1-2-3/h2H,1H2" liveInChI="yes">vinyl bromide</chemical> <XREF ID="chem17" TYPE="COMPOUND">17</XREF><REF ID="cit13" TYPE="P">13</REF> and Bu<SP><IT>t</IT></SP>Li followed by oxidation with IBX to provide the <chemical>ketone</chemical> <XREF ID="chem18" TYPE="COMPOUND">18</XREF> (60% from <XREF ID="chem16" TYPE="COMPOUND">16</XREF>). Its structure
was confirmed by IR (<IT>ν</IT> 1669 cm<SP>–1</SP>) and <SP>1</SP>H NMR data [<IT>δ</IT> 6.53 (1H, tq-like, <IT>J</IT> 5, 1, 10-H), 4.26 (2H, m, 11-<formula>H<SB>2</SB></formula>)]. Deprotection of the PMBM group in <XREF ID="chem18" TYPE="COMPOUND">18</XREF> with DDQ<REF ID="cit11b" TYPE="P">11<IT>b</IT></REF> gave the <chemical>alcohol</chemical> <XREF ID="chem19" TYPE="COMPOUND">19</XREF> (88%), which was treated with <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> and <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> to afford the <chemical>enolic β-diketone</chemical> <XREF ID="chem20" TYPE="COMPOUND">20</XREF> (36%) and the <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem21" TYPE="COMPOUND">21</XREF> (33%). Attempts to prepare <XREF ID="chem20" TYPE="COMPOUND">20</XREF> from <XREF ID="chem19" TYPE="COMPOUND">19</XREF> under other oxidation conditions (<IT>e.g.</IT>, <chemical>DMSO–oxalyl chloride</chemical>, DMSO–TFAA, DMSO–<formula>SO<SB>3</SB><B>·</B>Py</formula>, NMO–TPAP and IBX) were unsuccessful. The <SP>1</SP>H NMR spectrum of <XREF ID="chem20" TYPE="COMPOUND">20</XREF> had a broad
one-proton signal at <IT>δ</IT> 16.15 and a sharp one-proton resonance at <IT>δ</IT> 5.81. In addition, its IR spectrum showed an absorption at 1583 cm<SP>–1</SP> exhibiting the presence of a strongly hydrogen-bonded <chemical>carbonyl</chemical> group. These spectral data confirmed the presence of a completely <chemical>enolic β-diketone</chemical> structure. The structure of <XREF ID="chem21" TYPE="COMPOUND">21</XREF> was revealed by the following <SP>1</SP>H NMR data [an <chemical>acetoxy methyl</chemical> signal appeared at <IT>δ</IT> 2.14 (3H, s) and a <chemical SMILES="[H+]" InChI="InChI=1/p+1/i/hH">proton</chemical> signal (<IT>δ</IT> 4.23) due to C-6 shifted downfield compared to the corresponding signal (<IT>δ</IT> 4.04) of <XREF ID="chem19" TYPE="COMPOUND">19</XREF>].</P>
			<P>Unfortunately, direct conversion of <XREF ID="chem20" TYPE="COMPOUND">20</XREF> into the <chemical>C<SB>15</SB>-β-diketone aldehyde</chemical> <XREF ID="chem10a" TYPE="COMPOUND">10a</XREF> (Scheme 2) by deprotection of the <chemical>allylic</chemical> TBS group and subsequent oxidation of the resulting <chemical>alcohol</chemical> using several reagents (IBX, <formula><chemical>MnO<SB>2</SB></chemical></formula>, <IT>etc</IT>.) was unsuccessful, probably due to the instability of the <chemical>β-diketone</chemical> part. Thus, after protection of the <chemical>β-diketone</chemical> moiety in <XREF ID="chem20" TYPE="COMPOUND">20</XREF> by acetylation, the resulting <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem22" TYPE="COMPOUND">22</XREF> was partly deprotected with TBAF to give the <chemical>allylic alcohol</chemical> <XREF ID="chem23" TYPE="COMPOUND">23</XREF> (92%) which was oxidized with IBX followed by removal of another TBS group with <formula><chemical SMILES="[H]F" InChI="InChI=1/FH/h1H">HF</chemical></formula> to afford the <chemical>C<SB>15</SB>-aldehyde</chemical> <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF> (55% from <XREF ID="chem23" TYPE="COMPOUND">23</XREF>) as shown in Scheme 4. Its <SP>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>δ</IT> 10.17, d, <IT>J</IT> 7.5) and 10-H (<IT>δ</IT> 6.37, d, <IT>J</IT> 7.5).</P>
			
			<P>The Wittig reaction of <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF> with the <chemical>C<SB>10</SB>-phosphonium</chemical> salt <XREF ID="chem25" TYPE="COMPOUND">25</XREF><REF ID="cit14" TYPE="P">14</REF> in the presence of <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> as a base in a mixture of <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> and <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> gave condensed products which, after <chemical>acid</chemical> hydrolysis, provided an isomeric mixture of <chemical>C<SB>25</SB>-apocarotenals</chemical> <XREF ID="chem26" TYPE="COMPOUND">26</XREF> (92% from <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF>). Investigations of alternative conditions (<IT>e.g.</IT>, <formula><chemical>NaOMe–MeOH</chemical></formula>, Bu<SP><IT>n</IT></SP>Li–CH<SB>2</SB>Cl<SB>2</SB>–THF) for optimization of this condition resulted in the formation of an unexpected complex mixture. This is presumably owing to the presence of the conjugated <chemical>β-diketone</chemical> moiety in the molecule. It was notable that <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> was the best base in the condensation of the conjugated <chemical>polyenes</chemical> including the <chemical>β-diketone</chemical> part. Finally, the isomeric mixture <XREF ID="chem26" TYPE="COMPOUND">26</XREF> was condensed with the <chemical>acetylenic</chemical> C<SB>15</SB>-Wittig salt <XREF ID="chem27" TYPE="COMPOUND">27</XREF><REF ID="cit15" TYPE="P">15</REF> in the presence of <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> in <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> at 0 °C to yield the products (30%), a part of which was separated by repeated preparative HPLC (PHPLC) in the dark to afford all-<IT>E</IT> <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF>, 9<IT>Z</IT>-isomer <XREF ID="chem28" TYPE="COMPOUND">28</XREF>, <chemical>9<IT>Z</IT>,11<IT>Z</IT>-one</chemical> <XREF ID="chem29" TYPE="COMPOUND">29</XREF> and unidentified isomers. Three isomers (<XREF ID="chem1" TYPE="COMPOUND">1</XREF>, <XREF ID="chem28" TYPE="COMPOUND">28</XREF> and <XREF ID="chem29" TYPE="COMPOUND">29</XREF>) were respectively obtained in pure form (all-<IT>E</IT>
				<XREF ID="chem1" TYPE="COMPOUND">1</XREF>–9<IT>Z</IT>
				<XREF ID="chem28" TYPE="COMPOUND">28</XREF>–9<IT>Z</IT>,11<IT>Z</IT>
				<XREF ID="chem29" TYPE="COMPOUND">29</XREF>
				=
				<IT>ca.</IT>
1 ∶ 1 ∶ 1). Spectral data (UV–<formula>VIS</formula>, <SP>1</SP>H NMR and <formula><chemical>CD</chemical></formula>) of synthetic <chemical>mytiloxanthins</chemical> (all-<IT>E</IT> and 9<IT>Z</IT>-isomers) were in good agreement with those of natural specimens, respectively.<REF ID="cit4" TYPE="P">4</REF> Their configurations were confirmed from 2D-nuclear Overhauser enhancement spectroscopy (NOESY) experiments in <SP>1</SP>H NMR spectra (see Experimental section). 9<IT>Z</IT>,11<IT>Z</IT>-Stereochemistry in <XREF ID="chem29" TYPE="COMPOUND">29</XREF> was determined by <SP>1</SP>H NMR data in comparison with those<REF ID="cit16" TYPE="P">16</REF> of 9′<IT>Z</IT>,11′<IT>Z</IT>-isomer of <chemical>halocynthiaxanthin</chemical> <XREF ID="chem2" TYPE="COMPOUND">2</XREF> skeletal compound. This is the first biomimetic total synthesis of optically active all-<IT>E</IT> <chemical>mytiloxanthin</chemical> <XREF ID="chem1" TYPE="COMPOUND">1</XREF> by application of the stereoselective rearrangement of the <chemical>epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> with <chemical>aminium</chemical>
salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF>.</P>
		</DIV>
		<DIV><HEADER>Experimental</HEADER>
			<P>UV–<formula>VIS</formula> spectra were recorded on a JASCO Ubest-55 instrument for <chemical SMILES="OCC" InChI="InChI=1/C2H6O/c1-2-3/h3H,2H2,1H3" liveInChI="yes">ethanol</chemical> solutions unless otherwise stated. IR spectra were measured on a Perkin Elmer FT-IR spectrometer, model Paragon 1000, for <chemical SMILES="[H]C(Cl)(Cl)Cl" InChI="InChI=1/CHCl3/c2-1(3)4/h1H">chloroform</chemical> solutions. <SP>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 <chemical>deuteriochloroform</chemical> solutions (<chemical>tetramethylsilane</chemical> as internal reference). <IT>J</IT>-Values are given in Hz. NMR assignments are given 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>α</IT>]<SB>D</SB>-values are in units of 10<SP>–1</SP> deg cm<SP>2</SP> g<SP>–1</SP>). <formula><chemical>CD</chemical></formula> spectra were measured on a Shimadzu-AVIV 62A <formula><chemical>DS</chemical></formula> circular dichroism spectrometer.</P>
			<P>Column chromatography (<formula><chemical SMILES="[H]C1(CCC2([H])(C(CCCC12(C))=CC=C3CC(O)CCC3(=C)))(C(C)CCCC(C)C)" InChI="InChI=1/C27H44O/c1-19(2)8-6-9-21(4)25-15-16-26-22(10-7-17-27(25,26)5)12-13-23-18-24(28)14-11-20(23)3/h12-13,19,21,24-26,28H,3,6-11,14-18H2,1-2,4-5H3/b22-12+,23-13-/t21-,24+,25-,26+,27-/m1/s1">CC</chemical></formula>) was performed on <chemical>silica</chemical> gel (Merck Art. 7734). Short-column chromatography (<formula><chemical>SCC</chemical></formula>) was carried out on <chemical>silica</chemical> gel (Merck Art. 7739) under reduced pressure. Preparative TLC (PTLC) was conducted on <chemical>silica</chemical> gel <property type="nature"><quantity type="solidstate">plates</quantity></property> (Merck <chemical>silica</chemical> gel 60F<SB>254</SB> precoated <property type="nature"><quantity type="solidstate">plates</quantity></property>, <property type="quantity"><quantity type="conc"><value><point>0.5</point></value> mm</quantity></property> thickness). Low-pressure <formula><chemical SMILES="[H]C1(CCC2([H])(C(CCCC12(C))=CC=C3CC(O)CCC3(=C)))(C(C)CCCC(C)C)" InChI="InChI=1/C27H44O/c1-19(2)8-6-9-21(4)25-15-16-26-22(10-7-17-27(25,26)5)12-13-23-18-24(28)14-11-20(23)3/h12-13,19,21,24-26,28H,3,6-11,14-18H2,1-2,4-5H3/b22-12+,23-13-/t21-,24+,25-,26+,27-/m1/s1">CC</chemical></formula> was performed on a Yamazen Low Pressure <property type="nature"><quantity type="nonsolidstate">Liquid</quantity></property> Chromatography System using a Lobar column (Merck LiChroprep <formula><chemical Element="Si">Si</chemical></formula> 60). Analytical and PHPLC were carried out on Shimadzu LC-6A, or Waters 510 instruments with UV–<formula>VIS</formula> detectors.</P>
			<P>Standard work-up means that the organic layers or extracts were finally washed with <chemical>brine</chemical>, <property type="state">dried</property> over <property type="state">anhydrous</property> <chemical SMILES="[Na+].[Na+].O=S(=O)([O-])[O-]" InChI="InChI=1/2Na.H2O4S/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2">sodium sulfate</chemical> (<formula><chemical SMILES="[Na+].[Na+].O=S(=O)([O-])[O-]" InChI="InChI=1/2Na.H2O4S/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2">Na<SB>2</SB>SO<SB>4</SB></chemical></formula>), filtered and <property type="state">concentrated</property> <IT>in vacuo</IT> below <property type="quantity"><quantity type="temperature"><value><point>30</point></value> <units>°C</units></quantity></property> using a rotary evaporator. All operations were carried out under <chemical Element="N">nitrogen</chemical> or <chemical Element="Ar">argon</chemical>. <chemical SMILES="CCCCCC" InChI="InChI=1/C6H14/c1-3-5-6-4-2/h3-6H2,1-2H3">Hexane</chemical> refers to <chemical SMILES="CCCCCC" InChI="InChI=1/C6H14/c1-3-5-6-4-2/h3-6H2,1-2H3"><IT>n</IT>-hexane</chemical>.</P>
			<DIV><HEADER>Rearrangement of the <chemical>epoxide</chemical> <XREF ID="chem4" TYPE="COMPOUND">4</XREF> with <chemical>aminium</chemical> salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF></HEADER>
				<P>To a solution of <XREF ID="chem4" TYPE="COMPOUND">4</XREF> (<property type="quantity"><quantity type="mass"><value><point>142</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.5</point></value> <units>mmol</units></quantity></property>) in <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>1.5</point></value> <units>ml</units></quantity></property>) was added <chemical>aminium</chemical> salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF><REF ID="cit8" TYPE="P">8</REF> (<property type="quantity"><quantity type="mass"><value><point>8.17</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.01</point></value> <units>mmol</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>2</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. Evaporation of the reaction mixture gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 2 ∶ 3) to afford the <chemical>cyclopentyl</chemical> compound <XREF ID="chem7" TYPE="COMPOUND">7</XREF> <property type="yield"><quantity type="mass"><value><point>(98</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>69</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. Spectral data (IR and <SP>1</SP>H NMR) of this compound were in agreement with those of our previous report.<REF ID="cit5b" TYPE="P">5<IT>b</IT></REF></P>
			</DIV>
			<DIV><HEADER><chemical>2-[(4<IT>R</IT>)-4-<IT>tert</IT>-Butyldimethylsilyloxy-2,6,6-trimethylcyclohex-1-enyl]ethyl acetate</chemical> <XREF ID="chem12" TYPE="COMPOUND">12</XREF></HEADER>
				<P>To a solution of the <chemical>alcohol</chemical> <XREF ID="chem11" TYPE="COMPOUND">11</XREF><REF ID="cit1" TYPE="P">1</REF> (<property type="quantity"><quantity type="mass"><value><point>11.9</point></value> <units>g</units></quantity>, <quantity type="amount"><value><point>0.04</point></value> <units>mol</units></quantity></property>) in <property type="state">dry</property> Py (<property type="quantity"><quantity type="volume"><value><point>20</point></value> <units>ml</units></quantity></property>) was added <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> (<property type="quantity"><quantity type="volume"><value><point>15</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>16</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The mixture was poured into ice–water and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 9) to afford the <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem12" TYPE="COMPOUND">12</XREF> <property type="yield"><quantity type="mass"><value><point>(12.6</point></value> <units>g</units></quantity>, <quantity type="percent"><value><point>93</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; [<IT>α</IT>]26D
					–42.6 (<IT>c</IT> 1.22, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><peak><quantity type="vmax"><value><point>1732</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>340.2416</point></value></quantity>. <quantity type="formula">C<SB>19</SB>H<SB>36</SB>O<SB>3</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>340.2435</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER>2-[(1<IT>S</IT>,4<IT>S</IT>,6<IT>R</IT>)- and <chemical>(1<IT>R</IT>,4<IT>S</IT>,6<IT>S</IT>)-4-<IT>tert</IT>-Butyldimethylsilyloxy-2,2,6-trimethyl-7-oxabicyclo[4.1.0]heptan-1-yl]ethyl acetate</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> and <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF></HEADER>
				<P>A solution of MCPBA (72%, <property type="quantity"><quantity type="mass"><value><point>552</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>2.29</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) was added to an ice-cooled solution of the <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem12" TYPE="COMPOUND">12</XREF> (<property type="quantity"><quantity type="mass"><value><point>600</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>1.76</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>). After being stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>, the reaction mixture was diluted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> and washed successively with <property type="state">aq.</property> 1% <formula><chemical SMILES="[Na+].[Na+].O=S(=S)([O-])[O-]" InChI="InChI=1/2Na.H2O3S2/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2">Na<SB>2</SB>S<SB>2</SB>O<SB>3</SB></chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> solvent gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 5) followed by low-pressure <formula><chemical SMILES="[H]C1(CCC2([H])(C(CCCC12(C))=CC=C3CC(O)CCC3(=C)))(C(C)CCCC(C)C)" InChI="InChI=1/C27H44O/c1-19(2)8-6-9-21(4)25-15-16-26-22(10-7-17-27(25,26)5)12-13-23-18-24(28)14-11-20(23)3/h12-13,19,21,24-26,28H,3,6-11,14-18H2,1-2,4-5H3/b22-12+,23-13-/t21-,24+,25-,26+,27-/m1/s1">CC</chemical></formula> (<chemical>Et<SB>2</SB>O–benzene</chemical>, 1 ∶ 19) to afford the <chemical><IT>anti</IT>-epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> <property type="yield"><quantity type="mass"><value><point>(174</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>28</point></value></quantity>%)</property> and the <IT>syn</IT>- <chemical>epoxide</chemical> <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF> <property type="yield"><quantity type="mass"><value><point>(328</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>52</point></value></quantity>%)</property> as <property type="nature"><quantity type="colour">colorless</quantity></property> oils, respectively.</P>
				<DIV><HEADER><chemical><IT>anti</IT>-Epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF></HEADER><P>[<IT>α</IT>]22D
						–10.0 (<IT>c</IT> 1.00, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><peak><quantity type="vmax"><value><point>1733</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>356.2352</point></value></quantity>. <quantity type="formula">C<SB>19</SB>H<SB>38</SB>O<SB>4</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>356.2380</point></value></quantity>)</property>.</P>
				</DIV>
				<DIV><HEADER><chemical><IT>syn</IT>-Epoxide</chemical> <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF></HEADER><P>[<IT>α</IT>]22D
						–30.0 (<IT>c</IT> 1.00, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><peak><quantity type="vmax"><value><point>1733</point></value></quantity> (<quantity type="comment">OAc</quantity>)</peak></peaks></spectrum>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>356.2360</point></value></quantity>. <quantity type="formula">C<SB>19</SB>H<SB>36</SB>O<SB>4</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>356.2380</point></value></quantity>)</property>.</P>
				</DIV>
			</DIV>
			<DIV><HEADER>Conversion of <chemical>epoxide</chemical> <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF> to alkene <XREF ID="chem12" TYPE="COMPOUND">12</XREF></HEADER>
				<P>To a solution of <formula><chemical SMILES="[Na+].[I-]" InChI="InChI=1/HI.Na/h1H;/q;+1/p-1">NaI</chemical></formula> (<property type="quantity"><quantity type="mass"><value><point>1.35</point></value> <units>g</units></quantity>, <quantity type="amount"><value><point>9</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <chemical SMILES="CC#N" InChI="InChI=1/C2H3N/c1-2-3/h1H3">acetonitrile</chemical> (<property type="quantity"><quantity type="volume"><value><point>10</point></value> <units>ml</units></quantity></property>) was added <formula><chemical>TMSCl</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>0.56</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>4.5</point></value> <units>mmol</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for a few minutes. To this mixture was added a solution of the <chemical>epoxide</chemical> <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF> (<property type="quantity"><quantity type="mass"><value><point>1.07</point></value> <units>g</units></quantity>, <quantity type="amount"><value><point>3</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>, the reaction mixture was diluted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> and washed successively with <property type="state">aq.</property> 1% <formula><chemical SMILES="[Na+].[Na+].O=S(=S)([O-])[O-]" InChI="InChI=1/2Na.H2O3S2/c;;1-5(2,3)4/h;;(H2,1,2,3,4)/q2*+1;/p-2">Na<SB>2</SB>S<SB>2</SB>O<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> solvent gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 1 ∶ 4) to afford the <chemical>alcohol</chemical> <property type="yield"><quantity type="mass"><value><point>(542</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>80</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. To a solution of the <chemical>alcohol</chemical> (<property type="quantity"><quantity type="mass"><value><point>542</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>2.4</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) was added <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> (<property type="quantity"><quantity type="volume"><value><point>0.64</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>4.8</point></value> <units>mmol</units></quantity></property>), DMAP (<property type="quantity"><quantity type="mass"><value><point>586</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>4.8</point></value> <units>mmol</units></quantity></property>) and a solution of TBSCl (<property type="quantity"><quantity type="mass"><value><point>433</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>2.9</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>3</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>15</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture
was poured into ice–water and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 9) to yield <XREF ID="chem12" TYPE="COMPOUND">12</XREF> (<property type="quantity"><quantity type="mass"><value><point>611</point></value> <units>mg</units></quantity></property>, 75%; 60% from <XREF ID="chem5b" TYPE="COMPOUND">5b</XREF>) as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. Spectral data of this compound were identical with those of <XREF ID="chem12" TYPE="COMPOUND">12</XREF> derived from <XREF ID="chem11" TYPE="COMPOUND">11</XREF> in this paper.</P>
			</DIV>
			<DIV><HEADER>Rearrangement of <chemical>epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> by <chemical>aminium</chemical> salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF></HEADER>
				<P>To a solution of the <chemical>epoxide</chemical> <XREF ID="chem5a" TYPE="COMPOUND">5a</XREF> (<property type="quantity"><quantity type="mass"><value><point>178</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.5</point></value> <units>mmol</units></quantity></property>) in <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>4</point></value> <units>ml</units></quantity></property>) was added <chemical>aminium</chemical> salt <XREF ID="chem9" TYPE="COMPOUND">9</XREF><REF ID="cit8" TYPE="P">8</REF> (<property type="quantity"><quantity type="mass"><value><point>42</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.05</point></value> <units>mmol</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>. Evaporation of the reaction mixture gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 3 ∶ 17 → <chemical>acetone–hexane</chemical>, 1 ∶ 5) to afford the <chemical>cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF> <property type="yield"><quantity type="mass"><value><point>(112</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>63</point></value></quantity>%)</property> and the deprotected compound <XREF ID="chem13" TYPE="COMPOUND">13</XREF> <property type="yield"><quantity type="mass"><value><point>(36</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>30</point></value></quantity>%)</property> as <property type="nature"><quantity type="colour">colorless</quantity></property> oils, respectively.</P>
				<DIV><HEADER><chemical>Cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF></HEADER><P>[<IT>α</IT>]22D
						+10.0 (<IT>c</IT> 1.00, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>356.2356</point></value></quantity>. <quantity type="formula">C<SB>19</SB>H<SB>36</SB>O<SB>4</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>356.2380</point></value></quantity>)</property>.</P>
				</DIV>
				<DIV><HEADER>Deprotected compound <XREF ID="chem13" TYPE="COMPOUND">13</XREF></HEADER><P>[<IT>α</IT>]23D
						+5.00 (<IT>c</IT> 1.00, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>242.1535</point></value></quantity>. <quantity type="formula">C<SB>13</SB>H<SB>22</SB>O<SB>4</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>242.1519</point></value></quantity>)</property>.</P>
				</DIV>
			</DIV>
			<DIV><HEADER>Reprotection of the <chemical>alcohol</chemical> <XREF ID="chem13" TYPE="COMPOUND">13</XREF></HEADER>
				<P>To a solution of the <chemical>alcohol</chemical> <XREF ID="chem13" TYPE="COMPOUND">13</XREF> (<property type="quantity"><quantity type="mass"><value><point>145</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.60</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>3</point></value> <units>ml</units></quantity></property>) was added <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> (<property type="quantity"><quantity type="volume"><value><point>0.5</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>3.6</point></value> <units>mmol</units></quantity></property>), DMAP (<property type="quantity"><quantity type="mass"><value><point>110</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.90</point></value> <units>mmol</units></quantity></property>) and a solution of TBSCl (<property type="quantity"><quantity type="mass"><value><point>106</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.70</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>3</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>15</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture was poured into ice–water, and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 4) to afford <XREF ID="chem8" TYPE="COMPOUND">8</XREF> <property type="yield"><quantity type="mass"><value><point>(191</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>89</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. Spectral properties of this compound were in agreement with those of the <chemical>cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF> in the above rearrangement.</P>
			</DIV>
			<DIV><HEADER><chemical>3-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propyl acetate</chemical> <XREF ID="chem14" TYPE="COMPOUND">14</XREF></HEADER>
				<P>To a solution of the <chemical>cyclopentyl</chemical> compound <XREF ID="chem8" TYPE="COMPOUND">8</XREF> (<property type="quantity"><quantity type="mass"><value><point>255</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.72</point></value> <units>mmol</units></quantity></property>) in <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) was added <formula><chemical SMILES="[Na+].[BH4-]" InChI="InChI=1/BH4.Na/h1H4;/q-1;+1">NaBH<SB>4</SB></chemical></formula> (<property type="quantity"><quantity type="mass"><value><point>27.2</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.72</point></value> <units>mmol</units></quantity></property>) at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>. The reaction mixture was poured into ice–water, and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up afforded a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 5) to yield the <chemical>alcohol</chemical> <property type="yield"><quantity type="mass"><value><point>(200</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>78</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. Pr<SP><IT>i</IT></SP><SB>2</SB>NEt (<property type="quantity"><quantity type="volume"><value><point>0.98</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>5.60</point></value> <units>mmol</units></quantity></property>) and PMBMCl<REF ID="cit11" TYPE="P">11</REF> (<property type="quantity"><quantity type="mass"><value><point>626</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>3.36</point></value> <units>mmol</units></quantity></property>) were added to a solution of the above <chemical>alcohol</chemical> (<property type="quantity"><quantity type="mass"><value><point>200</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.56</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>2</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>16</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>, the reaction mixture was diluted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> and the organic layer was washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> solution gave a residue, which was purified
by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 1 ∶ 19) to afford the PMBM <chemical>ether</chemical> <XREF ID="chem14" TYPE="COMPOUND">14</XREF> (<property type="quantity"><quantity type="mass"><value><point>229</point></value> <units>mg</units></quantity></property>, 80%; 62% from <XREF ID="chem8" TYPE="COMPOUND">8</XREF>) as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>,
<quantity type="found"><value><point>508.3236</point></value></quantity>. <quantity type="formula">C<SB>28</SB>H<SB>48</SB>O<SB>6</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>508.3232</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>3-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propan-1-ol</chemical> <XREF ID="chem15" TYPE="COMPOUND">15</XREF></HEADER>
				<P>To a suspension of LAH (<property type="quantity"><quantity type="mass"><value><point>24</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.64</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) was added dropwise a solution of <XREF ID="chem14" TYPE="COMPOUND">14</XREF> (<property type="quantity"><quantity type="mass"><value><point>323</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.64</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>15</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>, the <property type="state">excess of</property> LAH was decomposed by dropwise addition of <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical>. The mixture was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> and the extracts were washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> solvent gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 1 ∶ 9) to afford the <chemical>alcohol</chemical> <XREF ID="chem15" TYPE="COMPOUND">15</XREF> <property type="yield"><quantity type="mass"><value><point>(292</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>99</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>466.3105</point></value></quantity>. <quantity type="formula">C<SB>26</SB>H<SB>46</SB>O<SB>5</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>466.3112</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>3-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-Butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-{[(4-methoxyphenyl)methoxy]methoxy}propanal</chemical> <XREF ID="chem16" TYPE="COMPOUND">16</XREF></HEADER>
				<P>To a solution of the <chemical>alcohol</chemical> <XREF ID="chem15" TYPE="COMPOUND">15</XREF> (<property type="quantity"><quantity type="mass"><value><point>125</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.27</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>) was added a solution of IBX<REF ID="cit12" TYPE="P">12</REF> (<property type="quantity"><quantity type="mass"><value><point>188</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.67</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>0.67</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture was diluted with <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) and the <property type="nature"><quantity type="colour">white</quantity></property> precipitate was filtered. The filtrate was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 1 ∶ 9) to provide the <chemical>aldehyde</chemical> <XREF ID="chem16" TYPE="COMPOUND">16</XREF> <property type="yield"><quantity type="mass"><value><point>(116</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>93</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>464.2967</point></value></quantity>. <quantity type="formula">C<SB>26</SB>H<SB>44</SB>O<SB>5</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>464.2960</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>(4<IT>E</IT>)-6-<IT>tert</IT>-Butyldimethylsilyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-1-{[(4-methoxyphenyl)methoxy]methoxy}-4-methylhex-4-en-3-one</chemical> <XREF ID="chem18" TYPE="COMPOUND">18</XREF></HEADER>
				<P>To a solution of the <chemical SMILES="C=CBr" InChI="InChI=1/C2H3Br/c1-2-3/h2H,1H2" liveInChI="yes">vinyl bromide</chemical> <XREF ID="chem17" TYPE="COMPOUND">17</XREF><REF ID="cit13" TYPE="P">13</REF> (<property type="quantity"><quantity type="mass"><value><point>403</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>1.52</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>4</point></value> <units>ml</units></quantity></property>) was added Bu<SP><IT>t</IT></SP>Li (<property type="quantity"><quantity type="conc"><value><point>1.64</point></value> M</quantity></property> in <chemical SMILES="CCCCC" InChI="InChI=1/C5H12/c1-3-5-4-2/h3-5H2,1-2H3">pentane</chemical>; <property type="quantity"><quantity type="volume"><value><point>0.93</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>1.52</point></value> <units>mmol</units></quantity></property>) at –<property type="quantity"><quantity type="temperature"><value><point>78</point></value> <units>°C</units></quantity></property> and the mixture was stirred at –<property type="quantity"><quantity type="temperature"><value><point>78</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>10</point></value> <units>min</units></quantity></property>. A solution of the <chemical>aldehyde</chemical> <XREF ID="chem16" TYPE="COMPOUND">16</XREF> (<property type="quantity"><quantity type="mass"><value><point>235</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.51</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>6</point></value> <units>ml</units></quantity></property>) was added to this mixture at –<property type="quantity"><quantity type="temperature"><value><point>78</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. After being quenched with <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[N+].[Cl-]" InChI="InChI=1/ClH.H3N/h1H;1H3">NH<SB>4</SB>Cl</chemical></formula>, the mixture was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 4) to afford the adduct <property type="yield"><quantity type="mass"><value><point>(313</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>95</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>. Then, to a solution of the adduct (<property type="quantity"><quantity type="mass"><value><point>313</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.48</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>1.5</point></value> <units>ml</units></quantity></property>) was added a solution of IBX<REF ID="cit12" TYPE="P">12</REF> (<property type="quantity"><quantity type="mass"><value><point>337</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>1.20</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>1.2</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>16</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction
mixture was diluted with <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> (<property type="quantity"><quantity type="volume"><value><point>5</point></value> <units>ml</units></quantity></property>) and the <property type="nature"><quantity type="colour">white</quantity></property> precipitate was filtered. The filtrate was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 3 ∶ 17) to provide the <property type="state">conjugated</property> <chemical>ketone</chemical> <XREF ID="chem18" TYPE="COMPOUND">18</XREF> (<property type="quantity"><quantity type="mass"><value><point>197</point></value> <units>mg</units></quantity></property>, 63%; 60% from <XREF ID="chem16" TYPE="COMPOUND">16</XREF>) as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>648.4236</point></value></quantity>. <quantity type="formula">C<SB>36</SB>H<SB>64</SB>O<SB>6</SB>Si<SB>2</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>648.4244</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>(4<IT>E</IT>)-6-<IT>tert</IT>-Butyldimethylsilyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-1-hydroxy-4-methylhex-4-en-3-one</chemical> <XREF ID="chem19" TYPE="COMPOUND">19</XREF></HEADER>
				<P>To a solution of the <chemical>ketone</chemical> <XREF ID="chem18" TYPE="COMPOUND">18</XREF> (<property type="quantity"><quantity type="mass"><value><point>197</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.30</point></value> <units>mmol</units></quantity></property>) dissolved in a mixture of <formula><chemical>CH<SB>2</SB>Cl<SB>2</SB>–H<SB>2</SB>O</chemical></formula> (18 ∶ 1, <property type="quantity"><quantity type="volume"><value><point>6.54</point></value> <units>ml</units></quantity></property>) was added DDQ<REF ID="cit11b" TYPE="P">11<IT>b</IT></REF> (<property type="quantity"><quantity type="mass"><value><point>86</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.36</point></value> <units>mmol</units></quantity></property>). After being stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>2</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>, the reaction mixture was filtered through <chemical>Celite</chemical>. Evaporation of the filtrate gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 9) to afford the <chemical>alcohol</chemical> <XREF ID="chem19" TYPE="COMPOUND">19</XREF> <property type="yield"><quantity type="mass"><value><point>(133</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>88</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>228</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>498.3531</point></value></quantity>. <quantity type="formula">C<SB>27</SB>H<SB>54</SB>O<SB>4</SB>Si<SB>2</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>498.3557</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER>Oxidation of the <chemical>β-hydroxy ketone</chemical> <XREF ID="chem19" TYPE="COMPOUND">19</XREF></HEADER>
				<P>To a solution of the <chemical>alcohol</chemical> <XREF ID="chem19" TYPE="COMPOUND">19</XREF> (<property type="quantity"><quantity type="mass"><value><point>200</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.40</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>14</point></value> <units>ml</units></quantity></property>) was added <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> (<property type="quantity"><quantity type="volume"><value><point>7</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>16</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture was poured into ice-water and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were washed with <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> and <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> solvent gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 19) to afford the <property type="state">conjugated</property> <chemical>β-diketone</chemical> <XREF ID="chem20" TYPE="COMPOUND">20</XREF> <property type="yield"><quantity type="mass"><value><point>(71</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>36</point></value></quantity>%)</property> and the <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem21" TYPE="COMPOUND">21</XREF> <property type="yield"><quantity type="mass"><value><point>(72</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>33</point></value></quantity>%)</property> as <property type="nature"><quantity type="colour">colorless</quantity></property> oils, respectively.</P>
				<DIV><HEADER><chemical>(2<IT>E</IT>,4<IT>E</IT>)-6-<IT>tert</IT>-Butyldimethylsilyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-3-hydroxy-4-methylhexa-2,4-dienone</chemical> <XREF ID="chem20" TYPE="COMPOUND">20</XREF></HEADER><P>[<IT>α</IT>]23D
						–23.4 (<IT>c</IT> 0.47, <formula><chemical SMILES="ClC(Cl)Cl" InChI="InChI=1/CHCl3/c2-1(3)4/h1H">CHCl<SB>3</SB></chemical></formula>); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>305</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><peak><quantity type="vmax"><value><point>1583</point></value></quantity> (<quantity type="comment">hydrogen-bonded conj. C�?O</quantity>)</peak></peaks></spectrum>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>496.3412</point></value></quantity>. <quantity type="formula">C<SB>27</SB>H<SB>52</SB>O<SB>4</SB>Si<SB>2</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>496.3407</point></value></quantity>)</property>.</P>
				</DIV>
				<DIV><HEADER><chemical>(4<IT>E</IT>)-1-Acetyloxy-6-<IT>tert</IT>-butyldimethylsilyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-4-methylhex-4-en-3-one</chemical> <XREF ID="chem21" TYPE="COMPOUND">21</XREF></HEADER><P>[<IT>α</IT>]27D
						+10.0 (<IT>c</IT> 0.40, <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>231</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><peak><quantity type="vmax"><value><point>1668</point></value></quantity> (<quantity type="comment">conj. C�?O</quantity>)</peak></peaks></spectrum>; <IT><IT>δ</IT></IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>α</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> <property type="hrms">[Found: (<quantity type="ion">M – Ac</quantity>)<SP>+</SP>, 497.3463. <quantity type="formula">C<SB>27</SB>H<SB>53</SB>O<SB>4</SB>Si<SB>2</SB></quantity> requires <quantity type="ion"><IT>M</IT>
						– Ac</quantity>, 497.3485]</property>.</P>
				</DIV>
			</DIV>
			<DIV><HEADER><chemical>(2<IT>E</IT>,4<IT>E</IT>)-3-Acetyloxy-6-<IT>tert</IT>-butyldimethylsilyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-4-methylhexa-2,4-dienone</chemical> <XREF ID="chem22" TYPE="COMPOUND">22</XREF></HEADER>
				<P><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> (<property type="quantity"><quantity type="volume"><value><point>0.5</point></value> <units>ml</units></quantity></property>) was added to a solution of the <chemical>β-diketone</chemical> <XREF ID="chem20" TYPE="COMPOUND">20</XREF> (<property type="quantity"><quantity type="mass"><value><point>104</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.21</point></value> <units>mmol</units></quantity></property>), <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> (<property type="quantity"><quantity type="volume"><value><point>0.04</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>0.29</point></value> <units>mmol</units></quantity></property>) and DMAP (<property type="quantity"><quantity type="mass"><value><point>28</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.23</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> <formula><chemical SMILES="ClCCl" InChI="InChI=1/CH2Cl2/c2-1-3/h1H2">CH<SB>2</SB>Cl<SB>2</SB></chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>, the mixture was poured into ice–water and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were washed successively with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>, <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 4) to afford the <chemical>enol acetate</chemical> <XREF ID="chem22" TYPE="COMPOUND">22</XREF> <property type="yield"><quantity type="mass"><value><point>(104</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>92</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; [<IT>α</IT>]20D
					–10.3 (<IT>c</IT> 0.98, <formula><chemical SMILES="ClC(Cl)Cl" InChI="InChI=1/CHCl3/c2-1(3)4/h1H">CHCl<SB>3</SB></chemical></formula>); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>277</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB>
(<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>β</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>538.3509</point></value></quantity>. <quantity type="formula">C<SB>29</SB>H<SB>54</SB>O<SB>5</SB>Si<SB>2</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>538.3512</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>(2<IT>E</IT>,4<IT>E</IT>)-3-Acetyloxy-1-[(1<IT>R</IT>,4<IT>S</IT>)-4-<IT>tert</IT>-butyldimethylsilyloxy-1,2,2-trimethylcyclopentyl]-6-hydroxy-4-methylhexa-2,4-dienone</chemical> <XREF ID="chem23" TYPE="COMPOUND">23</XREF></HEADER>
				<P>A solution of TBAF (<property type="quantity"><quantity type="conc"><value><point>1</point></value> M</quantity></property> in THF; <property type="quantity"><quantity type="volume"><value><point>0.19</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>0.19</point></value> <units>mmol</units></quantity></property>) was added to a solution of the <chemical SMILES="CC(=O)[O-]" InChI="InChI=1/C2H4O2/c1-2(3)4/h1H3,(H,3,4)/p-1">acetate</chemical> <XREF ID="chem22" TYPE="COMPOUND">22</XREF> (<property type="quantity"><quantity type="mass"><value><point>104</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.19</point></value> <units>mmol</units></quantity></property>) in <property type="state">dry</property> THF (<property type="quantity"><quantity type="volume"><value><point>4</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture was diluted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>Et<SB>2</SB>O–hexane</chemical>, 1 ∶ 4 → <chemical>acetone–hexane</chemical>, 1 ∶ 4) to afford the <chemical>alcohol</chemical> <XREF ID="chem23" TYPE="COMPOUND">23</XREF> <property type="yield"><quantity type="mass"><value><point>(75</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>92</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">colorless</quantity> <quantity type="nonsolidstate">oil</quantity></property>; [<IT>α</IT>]24D
					+0.98 (<IT>c</IT> 1.02, <formula><chemical SMILES="ClC(Cl)Cl" InChI="InChI=1/CHCl3/c2-1(3)4/h1H">CHCl<SB>3</SB></chemical></formula>); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>277</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>424.2632</point></value></quantity>. <quantity type="formula">C<SB>23</SB>H<SB>40</SB>O<SB>5</SB>Si</quantity> requires <IT>M</IT>, <quantity type="required"><value><point>424.2647</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>(2<IT>E</IT>,4<IT>E</IT>)-4-Acetyloxy-6-[(1<IT>R</IT>,4<IT>S</IT>)-4-hydroxy-1,2,2-trimethylcyclopentyl]-3-methyl-6-oxohexa-2,4-dienal</chemical> <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF></HEADER>
				<P>To a solution of the <chemical>alcohol</chemical> <XREF ID="chem23" TYPE="COMPOUND">23</XREF> (<property type="quantity"><quantity type="mass"><value><point>54</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.13</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>0.25</point></value> <units>ml</units></quantity></property>) was added a solution of IBX<REF ID="cit12" TYPE="P">12</REF> (<property type="quantity"><quantity type="mass"><value><point>72</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.26</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CS(=O)C" InChI="InChI=1/C2H6OS/c1-4(2)3/h1-2H3">DMSO</chemical> (<property type="quantity"><quantity type="volume"><value><point>0.26</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property> and the mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>. The reaction mixture was diluted with <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> (<property type="quantity"><quantity type="volume"><value><point>3</point></value> <units>ml</units></quantity></property>) and the <property type="nature"><quantity type="colour">white</quantity></property> precipitate was filtered. The filtrate was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 3 ∶ 17) to afford the <chemical>aldehyde</chemical> <property type="yield"><quantity type="mass"><value><point>(33</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>60</point></value></quantity>%)</property> as a <property type="nature"><quantity type="colour">pale</quantity> <quantity type="colour">yellow</quantity> <quantity type="nonsolidstate">oil</quantity></property>. A mixture of 47% <property type="state">aq</property> <formula><chemical>HF–CH<SB>3</SB>CN</chemical></formula> (1 ∶ 19; <property type="quantity"><quantity type="volume"><value><point>0.4</point></value> <units>ml</units></quantity></property>) was added to a solution of this <chemical>aldehyde</chemical> (<property type="quantity"><quantity type="mass"><value><point>33</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.08</point></value> <units>mmol</units></quantity></property>) in a mixture of CH<SB>3</SB>CN–THF (9 ∶ 1; <property type="quantity"><quantity type="volume"><value><point>4</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature">rt</quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>1.5</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>, the reaction mixture was quenched with <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. Standard work-up gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 3 ∶
7) to provide the desilylated <chemical>aldehyde</chemical> <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF> (<property type="quantity"><quantity type="mass"><value><point>22</point></value> <units>mg</units></quantity></property>, 92%; 55% from <XREF ID="chem23" TYPE="COMPOUND">23</XREF>) as a <property type="nature"><quantity type="colour">pale</quantity> <quantity type="colour">yellow</quantity> <quantity type="nonsolidstate">oil</quantity></property>; [<IT>α</IT>]26D
					–10.0 (<IT>c</IT> 0.40, <formula><chemical SMILES="ClC(Cl)Cl" InChI="InChI=1/CHCl3/c2-1(3)4/h1H">CHCl<SB>3</SB></chemical></formula>); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>283</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>308.1648</point></value></quantity>. <quantity type="formula">C<SB>17</SB>H<SB>24</SB>O<SB>5</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>308.1625</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER><chemical>(2<IT>E</IT>,4<IT>E</IT>,6<IT>E</IT>,8<IT>E</IT>,10<IT>E</IT>,12<IT>E</IT>)-12-Hydroxy-14-[(1<IT>R</IT>,4<IT>S</IT>)-4-hydroxy-1,2,2-trimethylcyclopentyl]-2,7,11-trimethyl-14-oxotetradeca-2,4,6,8,10,12-hexaenal</chemical> <XREF ID="chem26" TYPE="COMPOUND">26</XREF></HEADER>
				<P>An <property type="state">acidic</property> solution (<property type="quantity"><quantity type="volume"><value><point>0.1</point></value> <units>ml</units></quantity></property>) prepared from PTSA (<property type="quantity"><quantity type="mass"><value><point>500</point></value> <units>mg</units></quantity></property>) and <formula><chemical SMILES="[H]OP(=O)(O[H])O[H]" InChI="InChI=1/H3O4P/c1-5(2,3)4/h(H3,1,2,3,4)/f/h1-3H">H<SB>3</SB>PO<SB>4</SB></chemical></formula> (<property type="quantity"><quantity type="mass"><value><point>725</point></value> <units>mg</units></quantity></property>) in <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>37.5</point></value> <units>ml</units></quantity></property>) and <chemical>trimethyl orthoformate</chemical> (<property type="quantity"><quantity type="volume"><value><point>0.1</point></value> <units>ml</units></quantity>, <quantity type="amount"><value><point>0.91</point></value> <units>mmol</units></quantity></property>) were added to a solution of the Wittig salt <XREF ID="chem24" TYPE="COMPOUND">24</XREF><REF ID="cit14" TYPE="P">14</REF> (<property type="quantity"><quantity type="mass"><value><point>35.6</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.08</point></value> <units>mmol</units></quantity></property>) in <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula> (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>). The mixture was stirred at <property type="quantity"><quantity type="temperature">rt</quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property> and neutralized with <formula><chemical>NaOMe</chemical></formula> (<property type="quantity"><quantity type="conc"><value><point>1</point></value> M</quantity></property> in <formula><chemical SMILES="CO" InChI="InChI=1/CH4O/c1-2/h2H,1H3">MeOH</chemical></formula>) until just before the <property type="nature"><quantity type="colour">red</quantity></property> color of an <chemical>ylide</chemical> appeared. Evaporation of the solvent provided the Wittig salt <XREF ID="chem25" TYPE="COMPOUND">25</XREF>, to which a solution of the <chemical>aldehyde</chemical> <XREF ID="chem10b" TYPE="COMPOUND">10b</XREF> (<property type="quantity"><quantity type="mass"><value><point>9.8</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.03</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> (<property type="quantity"><quantity type="volume"><value><point>1.5</point></value> <units>ml</units></quantity></property>) was added. To the mixture, a <property type="state">basic</property> solution (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>) of <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> (<property type="quantity"><quantity type="mass"><value><point>500</point></value> <units>mg</units></quantity></property>) dissolved in <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>) and <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> (<property type="quantity"><quantity type="volume"><value><point>10</point></value> <units>ml</units></quantity></property>) was added dropwise at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>1</point></value> <units><chemical SMILES="[3He+]" InChI="InChI=1/He/q+2/i1-1">h</chemical></units></quantity></property>, the mixture was poured into ice–water, and extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula>. The extracts were shaken with <property type="state">aq.</property> 5% <formula><chemical SMILES="Cl" InChI="InChI=1/ClH/h1H">HCl</chemical></formula>
until the fine structure disappeared on UV–<formula>VIS</formula>, washed successively with <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[Na+].[H+].O=C([O-])[O-]" InChI="InChI=1/CH2O3.Na/c2-1(3)4;/h(H2,2,3,4);/q;+1/p-1">NaHCO<SB>3</SB></chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts provided a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 1 ∶ 4) to afford an isomeric mixture of <chemical>apocarotenal</chemical> <XREF ID="chem26" TYPE="COMPOUND">26</XREF> <property type="yield"><quantity type="mass"><value><point>(12</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>92</point></value></quantity>%)</property> in which the main product was all-<IT>E</IT> isomer. Purification of a part of the isomeric mixture by PTLC (<chemical>acetone–hexane</chemical>, 3 ∶ 7) provided the all-<IT>E</IT> isomer as an <property type="nature"><quantity type="colour">orange</quantity> <quantity type="solidstate">solid</quantity></property>; <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><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>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>300</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>398.2439</point></value></quantity>. <quantity type="formula">C<SB>25</SB>H<SB>34</SB>O<SB>4</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>398.2458</point></value></quantity>)</property>.</P>
			</DIV>
			<DIV><HEADER>Synthesis of <chemical>mytiloxanthin</chemical></HEADER>
				<P>A <property type="state">basic</property> solution (<property type="quantity"><quantity type="volume"><value><point>3</point></value> <units>ml</units></quantity></property>) of <formula><chemical SMILES="[K+].[O-]">KOH</chemical></formula> (<property type="quantity"><quantity type="mass"><value><point>500</point></value> <units>mg</units></quantity></property>) dissolved in <chemical SMILES="[H]O[H]" InChI="InChI=1/H2O/h1H2">water</chemical> (<property type="quantity"><quantity type="volume"><value><point>1</point></value> <units>ml</units></quantity></property>) and <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> (<property type="quantity"><quantity type="volume"><value><point>10</point></value> <units>ml</units></quantity></property>) was added dropwise to a solution of the <chemical>apocarotenal</chemical> <XREF ID="chem26" TYPE="COMPOUND">26</XREF> (<property type="quantity"><quantity type="mass"><value><point>11.7</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.03</point></value> <units>mmol</units></quantity></property>) and the Wittig salt <XREF ID="chem27" TYPE="COMPOUND">27</XREF><REF ID="cit15" TYPE="P">15</REF> (<property type="quantity"><quantity type="mass"><value><point>61</point></value> <units>mg</units></quantity>, <quantity type="amount"><value><point>0.12</point></value> <units>mmol</units></quantity></property>) in <chemical SMILES="CC(C)O" InChI="InChI=1/C3H8O/c1-3(2)4/h3-4H,1-2H3">propan-2-ol</chemical> (<property type="quantity"><quantity type="volume"><value><point>6</point></value> <units>ml</units></quantity></property>) at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property>. After being stirred at <property type="quantity"><quantity type="temperature"><value><point>0</point></value> <units>°C</units></quantity></property> for <property type="quantity"><quantity type="time"><value><point>30</point></value> <units>min</units></quantity></property>, the reaction mixture was extracted with <formula><chemical SMILES="CCOCC" InChI="InChI=1/C4H10O/c1-3-5-4-2/h3-4H2,1-2H3">Et<SB>2</SB>O</chemical></formula> and washed with <property type="state">saturated</property> <property type="state">aq.</property> <formula><chemical SMILES="[N+].[Cl-]" InChI="InChI=1/ClH.H3N/h1H;1H3">NH<SB>4</SB>Cl</chemical></formula> and <chemical>brine</chemical>. Evaporation of the <property type="state">dried</property> extracts gave a residue, which was purified by <formula><chemical>SCC</chemical></formula> (<chemical>acetone–hexane</chemical>, 3 ∶ 7) to afford an isomeric mixture of <chemical>mytiloxanthin</chemical> <property type="yield"><quantity type="mass"><value><point>(5.2</point></value> <units>mg</units></quantity>, <quantity type="percent"><value><point>30</point></value></quantity>%)</property>. Purification of a part of the isomeric mixture by PHPLC [CHEMCOSORB 7ODS-H 1.0 × 30 cm; <formula><chemical>H<SB>2</SB>O–MeOH</chemical></formula>, 4 ∶ 96; <property type="quantity"><quantity type="conc"><value><point>460</point></value> nm</quantity></property> detect.] provided the all-<IT>E</IT> isomer <XREF ID="chem1" TYPE="COMPOUND">1</XREF>, 9<IT>Z</IT> one <XREF ID="chem28" TYPE="COMPOUND">28</XREF> and
9<IT>Z</IT>,11<IT>Z</IT> one <XREF ID="chem29" TYPE="COMPOUND">29</XREF> as <property type="nature"><quantity type="colour">red</quantity></property> solids respectively, in a <property type="state">pure</property> state. Spectral properties of the synthetic all-<IT>E</IT> isomer <XREF ID="chem1" TYPE="COMPOUND">1</XREF> and 9<IT>Z</IT> one <XREF ID="chem28" TYPE="COMPOUND">28</XREF> were in agreement with those of a natural specimen.<REF ID="cit4" TYPE="P">4</REF></P>
				<DIV><HEADER>all-<IT>E</IT> Isomer <XREF ID="chem1" TYPE="COMPOUND">1</XREF></HEADER><P><chemical><formula>CD</formula> (<formula>Et<SB>2</SB>O</formula>)/nm</chemical> (Δ<IT>ε</IT>) 230 (–0.5), 275 (0), 294 (+0.7), 310 (0), 360 (–0.3); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>470</point></value></quantity></peak></peaks></spectrum>, <IT>λ</IT><spectrum type="uv"><SB>max</SB>(<quantity type="solvent">Et<SB>2</SB>O</quantity>)/nm <peaks type=".."><peak><quantity type="lmax"><value><point>467</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>598.4016</point></value></quantity>. <quantity type="formula">C<SB>40</SB>H<SB>54</SB>O<SB>4</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>598.4025</point></value></quantity>)</property>.</P>
				</DIV>
				<DIV><HEADER>9<IT>Z</IT>-Isomer <XREF ID="chem28" TYPE="COMPOUND">28</XREF></HEADER><P><chemical><formula>CD</formula> (<formula>Et<SB>2</SB>O</formula>)/nm</chemical> (Δ<IT>ε</IT>) 230 (–0.8), 247 (0), 258 (+1.0), 280 (0), 300 (–0.3), 310 (0), 350 (+1.0), 370 (0); <IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><peak><quantity type="lmax"><value><point>467</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>358</point></value></quantity></peak></peaks></spectrum> <IT>λ</IT><spectrum type="uv"><SB>max</SB>(<quantity type="solvent">Et<SB>2</SB>O</quantity>)/nm <peaks type=".."><peak><quantity type="lmax"><value><point>465</point></value></quantity></peak>, <peak><quantity type="lmax"><value><point>358</point></value></quantity></peak></peaks></spectrum>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> (the cross peak was observed between 11-H and 5-Me in the NOESY spectrum) <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>598.4001</point></value></quantity>. <quantity type="formula">C<SB>40</SB>H<SB>34</SB>O<SB>4</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>598.4025</point></value></quantity>)</property>.</P>
				</DIV>
				<DIV><HEADER>9<IT>Z</IT>,11<IT>Z</IT>-Isomer <XREF ID="chem29" TYPE="COMPOUND">29</XREF></HEADER><P><IT>λ</IT><spectrum type="uv"><SB>max</SB>/nm <peaks type=".."><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>, <IT>λ</IT><spectrum type="uv"><SB>max</SB>(<quantity type="solvent">Et<SB>2</SB>O</quantity>)/nm <peaks type=".."><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>; <IT>ν</IT><spectrum type="ir"><SB>max</SB>/cm<SP>–1</SP> <peaks type=".."><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>; <IT>δ</IT><spectrum type="hnmr"><SB>H</SB> (<quantity type="frequency"><value><point>500</point></value> <units>MHz</units></quantity>) <peaks type=".."><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>α</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>β</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>β</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>β</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>α</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>α</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> (the cross peak was observed between 11-H and 12-H in the NOESY spectrum) <property type="hrms">(Found: M<SP>+</SP>, <quantity type="found"><value><point>598.4018</point></value></quantity>. <quantity type="formula">C<SB>40</SB>H<SB>54</SB>O<SB>4</SB></quantity> requires <IT>M</IT>, <quantity type="required"><value><point>598.4025</point></value></quantity>)</property>.</P>
				</DIV>
			</DIV>
		</DIV>
	</BODY><ACKNOWLEDGMENTS>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>
		<REFERENCELIST><REFERENCE><AUTHORLIST><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>2001</YEAR><VOLUME/><ISSUE/><PAGES>3338</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>B. T.<SURNAME>Scheer</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Biol. Chem.</NAME><YEAR>1940</YEAR><VOLUME/><ISSUE/><PAGES>275</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>A. K.<SURNAME>Chopra</SURNAME></NAME></AUTHOR><AUTHOR><NAME>G. P.<SURNAME>Moss</SURNAME></NAME></AUTHOR><AUTHOR><NAME>B. C. L.<SURNAME>Weedon</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Chem. Commun.</NAME><YEAR>1977</YEAR><VOLUME/><ISSUE/><PAGES>467</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>A.
K.<SURNAME>Chopra</SURNAME></NAME></AUTHOR><AUTHOR><NAME>A.<SURNAME>Khare</SURNAME></NAME></AUTHOR><AUTHOR><NAME>G. P.<SURNAME>Moss</SURNAME></NAME></AUTHOR><AUTHOR><NAME>B. C. L.<SURNAME>Weedon</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1988</YEAR><VOLUME/><ISSUE/><PAGES>1383</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>B. C. L.<SURNAME>Weedon</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Pure Appl. Chem. Soc.</NAME><YEAR>1973</YEAR><VOLUME/><ISSUE/><PAGES>113</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>T.<SURNAME>Maoka</SURNAME></NAME></AUTHOR><AUTHOR><NAME>Y.<SURNAME>Fujiwara</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Jpn. Oil Chem. Soc.</NAME><YEAR>1996</YEAR><VOLUME/><ISSUE/><PAGES>667</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1996</YEAR><VOLUME/><ISSUE/><PAGES>1337</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1998</YEAR><VOLUME/><ISSUE/><PAGES>2569</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1999</YEAR><VOLUME/><ISSUE/><PAGES>1625</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>
						Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Chem. Pharm. Bull.</NAME><YEAR>2000</YEAR><VOLUME/><ISSUE/><PAGES>1833</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>L.<SURNAME>Lopez</SURNAME></NAME></AUTHOR><AUTHOR><NAME>G.<SURNAME>Mele</SURNAME></NAME></AUTHOR><AUTHOR><NAME>V.<SURNAME>Fiandanese</SURNAME></NAME></AUTHOR><AUTHOR><NAME>C.<SURNAME>Cardellicchio</SURNAME></NAME></AUTHOR><AUTHOR><NAME>A.<SURNAME>Nacci</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Tetrahedron</NAME><YEAR>1994</YEAR><VOLUME/><ISSUE/><PAGES>9097</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1993</YEAR><VOLUME/><ISSUE/><PAGES>1599</PAGES></JOURNAL></REFERENCE>
				<REFERENCE><AUTHORLIST><AUTHOR><NAME>R.<SURNAME>Caputo</SURNAME></NAME></AUTHOR><AUTHOR><NAME>L.<SURNAME>Mangoni</SURNAME></NAME></AUTHOR><AUTHOR><NAME>O.<SURNAME>Neri</SURNAME></NAME></AUTHOR><AUTHOR><NAME>G.<SURNAME>Palumbo</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Tetrahedron Lett.</NAME><YEAR>1981</YEAR><VOLUME/><ISSUE/><PAGES>3551</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>T.<SURNAME>Benneche</SURNAME></NAME></AUTHOR><AUTHOR><NAME>P.<SURNAME>Strande</SURNAME></NAME></AUTHOR><AUTHOR><NAME>K.<SURNAME>Undheim</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Synthesis</NAME><YEAR>1983</YEAR><VOLUME/><ISSUE/><PAGES>762</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>A. P.<SURNAME>Kozikowski</SURNAME></NAME></AUTHOR><AUTHOR><NAME>J.-P.<SURNAME>Wu</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Tetrahedron Lett.</NAME><YEAR>1987</YEAR><VOLUME/><ISSUE/><PAGES>5125</PAGES></JOURNAL></REFERENCE>
				<REFERENCE><AUTHORLIST><AUTHOR><NAME>M.<SURNAME>Frigerio</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Santagostino</SURNAME></NAME></AUTHOR><AUTHOR><NAME>S.<SURNAME>Sputore</SURNAME></NAME></AUTHOR><AUTHOR><NAME>G.<SURNAME>Palmisano</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Org. Chem.</NAME><YEAR>1995</YEAR><VOLUME/><ISSUE/><PAGES>7272</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>M.<SURNAME>Schlosser</SURNAME></NAME></AUTHOR><AUTHOR><NAME>E.<SURNAME>Hammer</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Helv. Chim. Acta</NAME><YEAR>1974</YEAR><VOLUME/><ISSUE/><PAGES>2547</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>A. R.<SURNAME>de Lera</SURNAME></NAME></AUTHOR><AUTHOR><NAME>B.<SURNAME>Iglesias</SURNAME></NAME></AUTHOR><AUTHOR><NAME>J.<SURNAME>Rodríguez</SURNAME></NAME></AUTHOR><AUTHOR><NAME>R.
							<SURNAME>Alvarez</SURNAME></NAME></AUTHOR><AUTHOR><NAME>S.<SURNAME>López</SURNAME></NAME></AUTHOR><AUTHOR><NAME>X.<SURNAME>Villanueva</SURNAME></NAME></AUTHOR><AUTHOR><NAME>E.<SURNAME>Padrós</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Am. Chem. Soc.</NAME><YEAR>1995</YEAR><VOLUME/><ISSUE/><PAGES>8220</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>K.<SURNAME>Bernhard</SURNAME></NAME></AUTHOR><AUTHOR><NAME>F.<SURNAME>Kienzle</SURNAME></NAME></AUTHOR><AUTHOR><NAME>H.<SURNAME>Mayer</SURNAME></NAME></AUTHOR><AUTHOR><NAME>R. K.<SURNAME>Müller</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Helv. Chim. Acta</NAME><YEAR>1980</YEAR><VOLUME/><ISSUE/><PAGES>1473</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>E.<SURNAME>Widmer</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Soukup</SURNAME></NAME></AUTHOR><AUTHOR><NAME>R.<SURNAME>Zell</SURNAME></NAME></AUTHOR><AUTHOR><NAME>E.<SURNAME>Broger</SURNAME></NAME></AUTHOR><AUTHOR><NAME>H. P.<SURNAME>Wagner</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Imfeld</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>Helv. Chim. Acta</NAME><YEAR>1990</YEAR><VOLUME/><ISSUE/><PAGES>861</PAGES></JOURNAL></REFERENCE><REFERENCE><AUTHORLIST><AUTHOR><NAME>Y.<SURNAME>Yamano</SURNAME></NAME></AUTHOR><AUTHOR><NAME>C.<SURNAME>Tode</SURNAME></NAME></AUTHOR><AUTHOR><NAME>M.<SURNAME>Ito</SURNAME></NAME></AUTHOR></AUTHORLIST><TITLE/><JOURNAL><NAME>J. Chem. Soc., Perkin Trans. 1</NAME><YEAR>1995</YEAR><VOLUME/><ISSUE/><PAGES>1895</PAGES></JOURNAL></REFERENCE></REFERENCELIST>
		<FOOTNOTELIST><FOOTNOTE ID="fn1" MARKER="1">We have employed the numbering system used in carotenoids.</FOOTNOTE></FOOTNOTELIST><FIGURELIST><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/><cmlPile><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></PAPER>
