Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides
Identifieur interne : 001963 ( Istex/Corpus ); précédent : 001962; suivant : 001964Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides
Auteurs : Naoyoshi Maezaki ; Mayuko Izumi ; Sachiko Yuyama ; Hiroaki Sawamoto ; Chuzo Iwata ; Tetsuaki TanakaSource :
- Tetrahedron [ 0040-4020 ] ; 2000.
English descriptors
- KwdEn :
- Acoet, Alkylation, Anal, Arch3, Brine, Calcd, Carbanions, Chcl3, Chem, Chromatographed, Colorless, Colorless powder, Cyclization, Diastereomeric, Diastereomeric mixture, Et3n, Ether, Evaporation, Geometric isomers, Hexane, Hrms, Intramolecular, Intramolecular alkylation, Isomer, Jeol, Maezaki, Mmol, Nahco3, Nh4cl, Och2o, Quenched, Racemization, Solvent evaporation, Sulfoxide, Sulfoxides, Tetrahedron, Thpoch2, Tosylate, Vinylic, Vinylic sulfoxide, Vinylic sulfoxides, alkylation, carbanions, cyclization, vinylic sulfoxides.
- Teeft :
- Acoet, Alkylation, Anal, Arch3, Brine, Calcd, Carbanions, Chcl3, Chem, Chromatographed, Colorless, Colorless powder, Cyclization, Diastereomeric, Diastereomeric mixture, Et3n, Ether, Evaporation, Geometric isomers, Hexane, Hrms, Intramolecular, Intramolecular alkylation, Isomer, Jeol, Maezaki, Mmol, Nahco3, Nh4cl, Och2o, Quenched, Racemization, Solvent evaporation, Sulfoxide, Sulfoxides, Tetrahedron, Thpoch2, Tosylate, Vinylic, Vinylic sulfoxide, Vinylic sulfoxides.
Abstract
Abstract: Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.
Url:
DOI: 10.1016/S0040-4020(00)00713-4
Links to Exploration step
ISTEX:067CC76E5F4B514597377303E5C615DD61343683Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title><author><name sortKey="Maezaki, Naoyoshi" sort="Maezaki, Naoyoshi" uniqKey="Maezaki N" first="Naoyoshi" last="Maezaki">Naoyoshi Maezaki</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Izumi, Mayuko" sort="Izumi, Mayuko" uniqKey="Izumi M" first="Mayuko" last="Izumi">Mayuko Izumi</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Yuyama, Sachiko" sort="Yuyama, Sachiko" uniqKey="Yuyama S" first="Sachiko" last="Yuyama">Sachiko Yuyama</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Sawamoto, Hiroaki" sort="Sawamoto, Hiroaki" uniqKey="Sawamoto H" first="Hiroaki" last="Sawamoto">Hiroaki Sawamoto</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Iwata, Chuzo" sort="Iwata, Chuzo" uniqKey="Iwata C" first="Chuzo" last="Iwata">Chuzo Iwata</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Tanaka, Tetsuaki" sort="Tanaka, Tetsuaki" uniqKey="Tanaka T" first="Tetsuaki" last="Tanaka">Tetsuaki Tanaka</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: t-tanaka@phs.osaka-u.ac.jp</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:067CC76E5F4B514597377303E5C615DD61343683</idno><date when="2000" year="2000">2000</date><idno type="doi">10.1016/S0040-4020(00)00713-4</idno><idno type="url">https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">001963</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">001963</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title><author><name sortKey="Maezaki, Naoyoshi" sort="Maezaki, Naoyoshi" uniqKey="Maezaki N" first="Naoyoshi" last="Maezaki">Naoyoshi Maezaki</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Izumi, Mayuko" sort="Izumi, Mayuko" uniqKey="Izumi M" first="Mayuko" last="Izumi">Mayuko Izumi</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Yuyama, Sachiko" sort="Yuyama, Sachiko" uniqKey="Yuyama S" first="Sachiko" last="Yuyama">Sachiko Yuyama</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Sawamoto, Hiroaki" sort="Sawamoto, Hiroaki" uniqKey="Sawamoto H" first="Hiroaki" last="Sawamoto">Hiroaki Sawamoto</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Iwata, Chuzo" sort="Iwata, Chuzo" uniqKey="Iwata C" first="Chuzo" last="Iwata">Chuzo Iwata</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation></author><author><name sortKey="Tanaka, Tetsuaki" sort="Tanaka, Tetsuaki" uniqKey="Tanaka T" first="Tetsuaki" last="Tanaka">Tetsuaki Tanaka</name><affiliation><mods:affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: t-tanaka@phs.osaka-u.ac.jp</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Tetrahedron</title><title level="j" type="abbrev">TET</title><idno type="ISSN">0040-4020</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2000">2000</date><biblScope unit="volume">56</biblScope><biblScope unit="issue">40</biblScope><biblScope unit="page" from="7927">7927</biblScope><biblScope unit="page" to="7945">7945</biblScope></imprint><idno type="ISSN">0040-4020</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0040-4020</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acoet</term><term>Alkylation</term><term>Anal</term><term>Arch3</term><term>Brine</term><term>Calcd</term><term>Carbanions</term><term>Chcl3</term><term>Chem</term><term>Chromatographed</term><term>Colorless</term><term>Colorless powder</term><term>Cyclization</term><term>Diastereomeric</term><term>Diastereomeric mixture</term><term>Et3n</term><term>Ether</term><term>Evaporation</term><term>Geometric isomers</term><term>Hexane</term><term>Hrms</term><term>Intramolecular</term><term>Intramolecular alkylation</term><term>Isomer</term><term>Jeol</term><term>Maezaki</term><term>Mmol</term><term>Nahco3</term><term>Nh4cl</term><term>Och2o</term><term>Quenched</term><term>Racemization</term><term>Solvent evaporation</term><term>Sulfoxide</term><term>Sulfoxides</term><term>Tetrahedron</term><term>Thpoch2</term><term>Tosylate</term><term>Vinylic</term><term>Vinylic sulfoxide</term><term>Vinylic sulfoxides</term><term>alkylation</term><term>carbanions</term><term>cyclization</term><term>vinylic sulfoxides</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Acoet</term><term>Alkylation</term><term>Anal</term><term>Arch3</term><term>Brine</term><term>Calcd</term><term>Carbanions</term><term>Chcl3</term><term>Chem</term><term>Chromatographed</term><term>Colorless</term><term>Colorless powder</term><term>Cyclization</term><term>Diastereomeric</term><term>Diastereomeric mixture</term><term>Et3n</term><term>Ether</term><term>Evaporation</term><term>Geometric isomers</term><term>Hexane</term><term>Hrms</term><term>Intramolecular</term><term>Intramolecular alkylation</term><term>Isomer</term><term>Jeol</term><term>Maezaki</term><term>Mmol</term><term>Nahco3</term><term>Nh4cl</term><term>Och2o</term><term>Quenched</term><term>Racemization</term><term>Solvent evaporation</term><term>Sulfoxide</term><term>Sulfoxides</term><term>Tetrahedron</term><term>Thpoch2</term><term>Tosylate</term><term>Vinylic</term><term>Vinylic sulfoxide</term><term>Vinylic sulfoxides</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.</div></front></TEI><istex><corpusName>elsevier</corpusName><keywords><teeft><json:string>mmol</json:string><json:string>calcd</json:string><json:string>hrms</json:string><json:string>chcl3</json:string><json:string>sulfoxide</json:string><json:string>sulfoxides</json:string><json:string>vinylic</json:string><json:string>acoet</json:string><json:string>alkylation</json:string><json:string>brine</json:string><json:string>solvent evaporation</json:string><json:string>chromatographed</json:string><json:string>tetrahedron</json:string><json:string>quenched</json:string><json:string>maezaki</json:string><json:string>intramolecular</json:string><json:string>vinylic sulfoxides</json:string><json:string>intramolecular alkylation</json:string><json:string>nahco3</json:string><json:string>chem</json:string><json:string>thpoch2</json:string><json:string>colorless</json:string><json:string>nh4cl</json:string><json:string>colorless powder</json:string><json:string>diastereomeric</json:string><json:string>isomer</json:string><json:string>et3n</json:string><json:string>och2o</json:string><json:string>ether</json:string><json:string>diastereomeric mixture</json:string><json:string>tosylate</json:string><json:string>anal</json:string><json:string>hexane</json:string><json:string>carbanions</json:string><json:string>vinylic sulfoxide</json:string><json:string>arch3</json:string><json:string>jeol</json:string><json:string>racemization</json:string><json:string>cyclization</json:string><json:string>geometric isomers</json:string><json:string>evaporation</json:string></teeft></keywords><author><json:item><name>Naoyoshi Maezaki</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string></affiliations></json:item><json:item><name>Mayuko Izumi</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string></affiliations></json:item><json:item><name>Sachiko Yuyama</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string></affiliations></json:item><json:item><name>Hiroaki Sawamoto</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string></affiliations></json:item><json:item><name>Chuzo Iwata</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string></affiliations></json:item><json:item><name>Tetsuaki Tanaka</name><affiliations><json:string>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</json:string><json:string>E-mail: t-tanaka@phs.osaka-u.ac.jp</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>vinylic sulfoxides</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>cyclization</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>alkylation</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>carbanions</value></json:item></subject><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.</abstract><qualityIndicators><score>6.464</score><pdfVersion>1.2</pdfVersion><pdfPageSize>595 x 794 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>4</keywordCount><abstractCharCount>862</abstractCharCount><pdfWordCount>15028</pdfWordCount><pdfCharCount>84257</pdfCharCount><pdfPageCount>19</pdfPageCount><abstractWordCount>122</abstractWordCount></qualityIndicators><title>Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title><pii><json:string>S0040-4020(00)00713-4</json:string></pii><genre><json:string>research-article</json:string></genre><host><title>Tetrahedron</title><language><json:string>unknown</json:string></language><publicationDate>2000</publicationDate><issn><json:string>0040-4020</json:string></issn><pii><json:string>S0040-4020(00)X0264-5</json:string></pii><volume>56</volume><issue>40</issue><pages><first>7927</first><last>7945</last></pages><genre><json:string>journal</json:string></genre></host><categories><wos><json:string>science</json:string><json:string>chemistry, organic</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>organic chemistry</json:string></scienceMetrix><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>agronomie. sciences du sol et productions vegetales</json:string></inist></categories><publicationDate>2000</publicationDate><copyrightDate>2000</copyrightDate><doi><json:string>10.1016/S0040-4020(00)00713-4</json:string></doi><id>067CC76E5F4B514597377303E5C615DD61343683</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>©2000 Elsevier Science Ltd</p></availability><date>2000</date></publicationStmt><notesStmt><note type="content">Scheme 1:</note><note type="content">Scheme 2: Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, −78°C; (b) Et3SiH, BF3·OEt2, CH2Cl2, 0°C→rt; (c) LDA, THF, −78°C; (d) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (e) MsCl, Et3N, CH2Cl2, 0°C→rt; (f) NaI, NaHCO3, acetone, reflux; (g) NaBr, NaHCO3, acetone, reflux; (h) LiCl, acetone, reflux; (i) Dess–Martin periodinane, CH2Cl2, rt; (j) MeMgBr, THF, 0°C.</note><note type="content">Scheme 3: Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, −78°C; (b) NaBH4, MeOH, 0°C; (c) MsCl, Et3N, CH2Cl2, 0°C→rt; (d) t-BuOK, THF, 0°C→rt; (e) NaI, NaHCO3, acetone, reflux.</note><note type="content">Scheme 4: Reagents and conditions: (a) EtMgBr, ether, 0°C→reflux then (S)-(−)-menthyl p-toluenesulfinate, toluene, 0°C; (b) H2, RhCl(PPh3)3, benzene, rt; (c) HF·pyridine, THF–pyridine=1:1, rt; (d) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (e) NaI, NaHCO3, acetone, reflux.</note><note type="content">Scheme 5: Reagents and conditions: (a) p-TsCl, Et3N, DMAP CH2Cl2, 0°C→rt; (b) Dess–Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (d) NaI, NaHCO3, acetone, reflux; (e) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C→rt; (f) p-TsOH·H2O, MeOH, rt.</note><note type="content">Scheme 6: Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (b) LDA, THF, −78°C then H2O.</note><note type="content">Scheme 7: Reagents and conditions: (a) DHP, PPTS, CH2Cl2, rt; (b) Dess–Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (d) p-TsOH·H2O, MeOH, rt; (e) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (f) NaBr, DMF/CH2Br2=2:1, 100°C; (g) NaI, NaHCO3, acetone, rt; (h) LDA, THF, −78°C.</note><note type="content">Scheme 8: Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C→rt; (b) LDA, THF, −78°C; (c) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (d) NaI, NaHCO3, acetone, reflux; (e) MOMCl, i-PrNEt2, CH2Cl2, rt; (f) HF·pyridine, THF–pyridine=1:1, rt.</note><note type="content">Table 1: Intramolecular alkylation of vinylic sulfoxide (E)-11 (the substrate was treated with 1.5equiv. of the base at −78°C under N2)</note><note type="content">Table 2: Cyclization of vinylic sulfoxides and the optical purities of the products (the substrate was treated with 1.5equiv. of LDA in THF at −78°C under N2)</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title><author xml:id="author-0000"><persName><forename type="first">Naoyoshi</forename><surname>Maezaki</surname></persName><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><author xml:id="author-0001"><persName><forename type="first">Mayuko</forename><surname>Izumi</surname></persName><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><author xml:id="author-0002"><persName><forename type="first">Sachiko</forename><surname>Yuyama</surname></persName><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><author xml:id="author-0003"><persName><forename type="first">Hiroaki</forename><surname>Sawamoto</surname></persName><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><author xml:id="author-0004"><persName><forename type="first">Chuzo</forename><surname>Iwata</surname></persName><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><author xml:id="author-0005"><persName><forename type="first">Tetsuaki</forename><surname>Tanaka</surname></persName><email>t-tanaka@phs.osaka-u.ac.jp</email><note type="correspondence"><p>Corresponding author. Tel.: +81-6-6879-8210; fax: +81-6-6879-8214</p></note><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation></author><idno type="istex">067CC76E5F4B514597377303E5C615DD61343683</idno><idno type="DOI">10.1016/S0040-4020(00)00713-4</idno><idno type="PII">S0040-4020(00)00713-4</idno></analytic><monogr><title level="j">Tetrahedron</title><title level="j" type="abbrev">TET</title><idno type="pISSN">0040-4020</idno><idno type="PII">S0040-4020(00)X0264-5</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2000"></date><biblScope unit="volume">56</biblScope><biblScope unit="issue">40</biblScope><biblScope unit="page" from="7927">7927</biblScope><biblScope unit="page" to="7945">7945</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2000</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>Keywords</head><item><term>vinylic sulfoxides</term></item><item><term>cyclization</term></item><item><term>alkylation</term></item><item><term>carbanions</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2000">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="sc1" NDATA="IMAGE" name="sc1"></istex:entity><istex:entity SYSTEM="sc2" NDATA="IMAGE" name="sc2"></istex:entity><istex:entity SYSTEM="sc3" NDATA="IMAGE" name="sc3"></istex:entity><istex:entity SYSTEM="sc4" NDATA="IMAGE" name="sc4"></istex:entity><istex:entity SYSTEM="sc5" NDATA="IMAGE" name="sc5"></istex:entity><istex:entity SYSTEM="fx1" NDATA="IMAGE" name="fx1"></istex:entity><istex:entity SYSTEM="fx2" NDATA="IMAGE" name="fx2"></istex:entity><istex:entity SYSTEM="sc6" NDATA="IMAGE" name="sc6"></istex:entity><istex:entity SYSTEM="sc7" NDATA="IMAGE" name="sc7"></istex:entity><istex:entity SYSTEM="sc8" NDATA="IMAGE" name="sc8"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla" xml:lang="en"><item-info><jid>TET</jid><aid>8495</aid><ce:pii>S0040-4020(00)00713-4</ce:pii><ce:doi>10.1016/S0040-4020(00)00713-4</ce:doi><ce:copyright type="full-transfer" year="2000">Elsevier Science Ltd</ce:copyright></item-info><head><ce:title>Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</ce:title><ce:author-group><ce:author><ce:given-name>Naoyoshi</ce:given-name><ce:surname>Maezaki</ce:surname></ce:author><ce:author><ce:given-name>Mayuko</ce:given-name><ce:surname>Izumi</ce:surname></ce:author><ce:author><ce:given-name>Sachiko</ce:given-name><ce:surname>Yuyama</ce:surname></ce:author><ce:author><ce:given-name>Hiroaki</ce:given-name><ce:surname>Sawamoto</ce:surname></ce:author><ce:author><ce:given-name>Chuzo</ce:given-name><ce:surname>Iwata</ce:surname></ce:author><ce:author><ce:given-name>Tetsuaki</ce:given-name><ce:surname>Tanaka</ce:surname><ce:cross-ref refid="CORR1">*</ce:cross-ref><ce:e-address>t-tanaka@phs.osaka-u.ac.jp</ce:e-address></ce:author><ce:affiliation><ce:textfn>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +81-6-6879-8210; fax: +81-6-6879-8214</ce:text></ce:correspondence></ce:author-group><ce:date-received day="23" month="6" year="2000"></ce:date-received><ce:date-accepted day="10" month="8" year="2000"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (<ce:italic>E</ce:italic>)-isomer but also the (<ce:italic>Z</ce:italic>)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword" xml:lang="en"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>vinylic sulfoxides</ce:text></ce:keyword><ce:keyword><ce:text>cyclization</ce:text></ce:keyword><ce:keyword><ce:text>alkylation</ce:text></ce:keyword><ce:keyword><ce:text>carbanions</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title></titleInfo><titleInfo type="alternative" lang="en" contentType="CDATA"><title>Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides</title></titleInfo><name type="personal"><namePart type="given">Naoyoshi</namePart><namePart type="family">Maezaki</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Mayuko</namePart><namePart type="family">Izumi</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Sachiko</namePart><namePart type="family">Yuyama</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Hiroaki</namePart><namePart type="family">Sawamoto</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Chuzo</namePart><namePart type="family">Iwata</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Tetsuaki</namePart><namePart type="family">Tanaka</namePart><affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation><affiliation>E-mail: t-tanaka@phs.osaka-u.ac.jp</affiliation><description>Corresponding author. Tel.: +81-6-6879-8210; fax: +81-6-6879-8214</description><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-1JC4F85T-7">research-article</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">2000</dateIssued><copyrightDate encoding="w3cdtf">2000</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><abstract lang="en">Abstract: Intramolecular alkylation of various β-(ω-haloalkyl) substituted vinylic sulfoxides was investigated. Upon treatment with LDA in THF at −78°C, α-sulfinyl carbanion generated from vinylic sulfoxides cyclized at the α-sulfinyl position to give 1-cycloalkenyl sulfoxides with a five- to seven-membered ring. Although iodide or bromide is normally a good leaving group, chloride affords better results than the corresponding iodide and bromide when the reaction takes place at the benzylic position. The cyclization proceeded even with the secondary iodide in moderate yield. Not only the (E)-isomer but also the (Z)-isomer cyclized via rapid inversion of the olefin geometry. No loss of optical purity was observed during isomerization. Various 1-cycloalkenyl sulfoxides including a fused ring and a polyoxygenated rings were synthesized in good to moderate yields.</abstract><note type="content">Scheme 1: </note><note type="content">Scheme 2: Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, −78°C; (b) Et3SiH, BF3·OEt2, CH2Cl2, 0°C→rt; (c) LDA, THF, −78°C; (d) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (e) MsCl, Et3N, CH2Cl2, 0°C→rt; (f) NaI, NaHCO3, acetone, reflux; (g) NaBr, NaHCO3, acetone, reflux; (h) LiCl, acetone, reflux; (i) Dess–Martin periodinane, CH2Cl2, rt; (j) MeMgBr, THF, 0°C.</note><note type="content">Scheme 3: Reagents and conditions: (a) LDA, (R)-methyl tolyl sulfoxide, THF, −78°C; (b) NaBH4, MeOH, 0°C; (c) MsCl, Et3N, CH2Cl2, 0°C→rt; (d) t-BuOK, THF, 0°C→rt; (e) NaI, NaHCO3, acetone, reflux.</note><note type="content">Scheme 4: Reagents and conditions: (a) EtMgBr, ether, 0°C→reflux then (S)-(−)-menthyl p-toluenesulfinate, toluene, 0°C; (b) H2, RhCl(PPh3)3, benzene, rt; (c) HF·pyridine, THF–pyridine=1:1, rt; (d) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (e) NaI, NaHCO3, acetone, reflux.</note><note type="content">Scheme 5: Reagents and conditions: (a) p-TsCl, Et3N, DMAP CH2Cl2, 0°C→rt; (b) Dess–Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (d) NaI, NaHCO3, acetone, reflux; (e) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C→rt; (f) p-TsOH·H2O, MeOH, rt.</note><note type="content">Scheme 6: Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (b) LDA, THF, −78°C then H2O.</note><note type="content">Scheme 7: Reagents and conditions: (a) DHP, PPTS, CH2Cl2, rt; (b) Dess–Martin periodinane, CH2Cl2, rt; (c) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C; (d) p-TsOH·H2O, MeOH, rt; (e) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (f) NaBr, DMF/CH2Br2=2:1, 100°C; (g) NaI, NaHCO3, acetone, rt; (h) LDA, THF, −78°C.</note><note type="content">Scheme 8: Reagents and conditions: (a) n-BuLi, (MeO)2P(O)CH2S∗(O)Tol, THF, −78°C→rt; (b) LDA, THF, −78°C; (c) p-TsCl, Et3N, DMAP, CH2Cl2, 0°C→rt; (d) NaI, NaHCO3, acetone, reflux; (e) MOMCl, i-PrNEt2, CH2Cl2, rt; (f) HF·pyridine, THF–pyridine=1:1, rt.</note><note type="content">Table 1: Intramolecular alkylation of vinylic sulfoxide (E)-11 (the substrate was treated with 1.5equiv. of the base at −78°C under N2)</note><note type="content">Table 2: Cyclization of vinylic sulfoxides and the optical purities of the products (the substrate was treated with 1.5equiv. of LDA in THF at −78°C under N2)</note><subject lang="en"><genre>Keywords</genre><topic>vinylic sulfoxides</topic><topic>cyclization</topic><topic>alkylation</topic><topic>carbanions</topic></subject><relatedItem type="host"><titleInfo><title>Tetrahedron</title></titleInfo><titleInfo type="abbreviated"><title>TET</title></titleInfo><genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">20000929</dateIssued></originInfo><identifier type="ISSN">0040-4020</identifier><identifier type="PII">S0040-4020(00)X0264-5</identifier><part><date>20000929</date><detail type="volume"><number>56</number><caption>vol.</caption></detail><detail type="issue"><number>40</number><caption>no.</caption></detail><extent unit="issue-pages"><start>7829</start><end>8032</end></extent><extent unit="pages"><start>7927</start><end>7945</end></extent></part></relatedItem><identifier type="istex">067CC76E5F4B514597377303E5C615DD61343683</identifier><identifier type="ark">ark:/67375/6H6-7F4GHG2C-F</identifier><identifier type="DOI">10.1016/S0040-4020(00)00713-4</identifier><identifier type="PII">S0040-4020(00)00713-4</identifier><accessCondition type="use and reproduction" contentType="copyright">©2000 Elsevier Science Ltd</accessCondition><recordInfo><recordContentSource authority="ISTEX" authorityURI="https://loaded-corpus.data.istex.fr" valueURI="https://loaded-corpus.data.istex.fr/ark:/67375/XBH-HKKZVM7B-M">elsevier</recordContentSource><recordOrigin>Elsevier Science Ltd, ©2000</recordOrigin></recordInfo></mods><json:item><extension>json</extension><original>false</original><mimetype>application/json</mimetype><uri>https://api.istex.fr/document/067CC76E5F4B514597377303E5C615DD61343683/metadata/json</uri></json:item></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Lorraine/explor/LrgpV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 001963 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 001963 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Lorraine
|area= LrgpV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:067CC76E5F4B514597377303E5C615DD61343683
|texte= Studies on Intramolecular Alkylation of an α-Sulfinyl Vinylic Carbanion: a Novel Route to Chiral 1-Cycloalkenyl Sulfoxides
}}
| This area was generated with Dilib version V0.6.32. |  |