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
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<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>
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<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>
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<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>
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<note type="correspondence"><p>Corresponding author. Tel.: +81-6-6879-8210; fax: +81-6-6879-8214</p>
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<affiliation>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</affiliation>
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<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>
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<item><term>cyclization</term>
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<item><term>carbanions</term>
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<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>
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<ce:author><ce:given-name>Mayuko</ce:given-name>
<ce:surname>Izumi</ce:surname>
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<ce:author><ce:given-name>Sachiko</ce:given-name>
<ce:surname>Yuyama</ce:surname>
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<ce:author><ce:given-name>Hiroaki</ce:given-name>
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<ce:author><ce:given-name>Chuzo</ce:given-name>
<ce:surname>Iwata</ce:surname>
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<ce:author><ce:given-name>Tetsuaki</ce:given-name>
<ce:surname>Tanaka</ce:surname>
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<ce:e-address>t-tanaka@phs.osaka-u.ac.jp</ce:e-address>
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<ce:affiliation><ce:textfn>Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan</ce:textfn>
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<ce:correspondence id="CORR1"><ce:label>*</ce:label>
<ce:text>Corresponding author. Tel.: +81-6-6879-8210; fax: +81-6-6879-8214</ce:text>
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<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>
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<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>
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<ce:keyword><ce:text>carbanions</ce:text>
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<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>
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