Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by P[superscript III]/Psuperscript V]=O Redox Cycling
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nihms-1006607.pdf
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Author(s)
Ghosh, Avipsa
Lecomte, Morgan C
Kim‐Lee, Shin‐Ho
Radosevich, Alexander T.
Date Issued
February 2019
Journal
Angewandte Chemie International Edition
Publisher
Wiley
Citation
Ghosh, Avipsa et al. “Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by P[superscript III]/Psuperscript V]=O Redox Cycling.” Angewandte Chemie - International Edition, vol. 58, no. 9, 2019, pp. 2864-2869 © 2019 The Author(s)
Version
Author's final manuscript
Abstract
A method for electrophilic sulfenylation by organophosphorus-catalyzed deoxygenative O-atom transfer from sulfonyl chlorides is reported. This C−S bond-forming reaction is catalyzed by a readily available small-ring phosphine (phosphetane) in conjunction with a hydrosilane terminal reductant to afford a general entry to sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives that are otherwise difficult to access. Mechanistic investigations indicate that the twofold deoxygenation of the sulfonyl substrate proceeds by the intervention of an off-cycle resting state thiophosphonium ion. The catalytic method represents an operationally simple protocol using a stable phosphine oxide as a precatalyst and exhibits broad functional-group tolerance.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1002/anie.201813919
