Organophosphorus‐Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling. Issue 9 (25th January 2019)

• Record Type: Journal Article
• Authors: Ghosh, Avipsa; Lecomte, Morgan; Kim‐Lee, Shin‐Ho; Radosevich, Alexander T.
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 9(2019)
• Page Start: 2864
• Page End: 2869
• Publication Date: 2019-01-25
• Subjects: organocatalysis -- phosphorus -- reaction mechanisms -- redox chemistry -- sulfenylation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201813919
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Oat field : A method for electrophilic sulfenylation by organophosphorus‐catalyzed deoxygenative O‐atom transfer (OAT) from sulfonyl chlorides is reported. This C−S bond‐forming reaction is catalyzed by 1 (phosphetane) in conjunction with a hydrosilane terminal reductant to afford sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives.