Solvent-Driven Mono- and Bis-sulfenylation of (E)‑β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes
The nature of solvent is a key factor for stereoselective mono- and bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-β-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick a...
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Veröffentlicht in: | Journal of organic chemistry 2022-03, Vol.87 (6), p.3934-3951 |
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creator | Reddy, Raju Jannapu Kumari, Arram Haritha Sharadha, Nunavath Krishna, Gamidi Rama |
description | The nature of solvent is a key factor for stereoselective mono- and bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-β-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments. |
doi_str_mv | 10.1021/acs.joc.1c02444 |
format | Article |
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A novel and unprecedented vicinal bisthiolation of (E)-β-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. 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Org. Chem</addtitle><description>The nature of solvent is a key factor for stereoselective mono- and bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-β-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.</description><subject>Alkenes</subject><subject>Dimethyl Sulfoxide</subject><subject>Solvents</subject><subject>Stereoisomerism</subject><subject>Sulfhydryl Compounds</subject><subject>Sulfones</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp1kc1OGzEUhS0EIiFlza7yMlXrxP8zWbZAChKIRdL1aH7uKAbHhvEMbXa8Ag_AS_RB-hB9knpIyg5vjuT7nXNlH4ROGJ0wytk0L8Pk1pcTVlIupdxDQ6Y4JXpG5T4aUso5EVyLAToK4ZbGo5Q6RAOhuFQ0oUP0svD2EVxLzhoTFV975wnOXYW_mUBCZ2twG5u3xjvsazw-__T36fnPb3LpK_9o4ggvIuMdBPzTtCu8XBlvA659g-cWfpnCAl5sXLuCYEKfwL5w0kPh1Raj7R307n5lPzuLKcbvbj-ggzq3AY53OkI_5ufL0wtydfP98vTrFcmFEC3RoKguGKhEK86LmUxLqHXKC0jyKGkh0lRLSQWX1UzWvKK0TBjTuk5kVdFSjNB4m3vf-IcOQputTSjB2tyB70IWv1AzmSipIjrdomXjQ2igzu4bs86bTcZo1neSxU6y2Em26yQ6Pu7Cu2IN1Rv_v4QIfN4CW2fXuPjWd-P-Afw6mUE</recordid><startdate>20220318</startdate><enddate>20220318</enddate><creator>Reddy, Raju Jannapu</creator><creator>Kumari, Arram Haritha</creator><creator>Sharadha, Nunavath</creator><creator>Krishna, Gamidi Rama</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-0667-6787</orcidid></search><sort><creationdate>20220318</creationdate><title>Solvent-Driven Mono- and Bis-sulfenylation of (E)‑β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes</title><author>Reddy, Raju Jannapu ; Kumari, Arram Haritha ; Sharadha, Nunavath ; Krishna, Gamidi Rama</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a333t-6e506b1e576522b948cef682be7a6828b3886440324d94f2d00c71166f74dd0c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Alkenes</topic><topic>Dimethyl Sulfoxide</topic><topic>Solvents</topic><topic>Stereoisomerism</topic><topic>Sulfhydryl Compounds</topic><topic>Sulfones</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Reddy, Raju Jannapu</creatorcontrib><creatorcontrib>Kumari, Arram Haritha</creatorcontrib><creatorcontrib>Sharadha, Nunavath</creatorcontrib><creatorcontrib>Krishna, Gamidi Rama</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Reddy, Raju Jannapu</au><au>Kumari, Arram Haritha</au><au>Sharadha, Nunavath</au><au>Krishna, Gamidi Rama</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Solvent-Driven Mono- and Bis-sulfenylation of (E)‑β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2022-03-18</date><risdate>2022</risdate><volume>87</volume><issue>6</issue><spage>3934</spage><epage>3951</epage><pages>3934-3951</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>The nature of solvent is a key factor for stereoselective mono- and bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-β-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>35245070</pmid><doi>10.1021/acs.joc.1c02444</doi><tpages>18</tpages><orcidid>https://orcid.org/0000-0002-0667-6787</orcidid></addata></record> |
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subjects | Alkenes Dimethyl Sulfoxide Solvents Stereoisomerism Sulfhydryl Compounds Sulfones |
title | Solvent-Driven Mono- and Bis-sulfenylation of (E)‑β-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes |
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