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
Hauptverfasser: Reddy, Raju Jannapu, Kumari, Arram Haritha, Sharadha, Nunavath, Krishna, Gamidi Rama
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container_end_page 3951
container_issue 6
container_start_page 3934
container_title Journal of organic chemistry
container_volume 87
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
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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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