Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by P[superscript III]/Psuperscript V]=O Redox Cycling
Author(s)Ghosh, Avipsa; Lecomte, Morgan C; Kim‐Lee, Shin‐Ho; Radosevich, Alexander T.
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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.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Angewandte Chemie International Edition
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)
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