Organophosphorus‐Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling

• Published in: Angewandte Chemie International Edition Vol. 58; no. 9; pp. 2864 - 2869
• Main Authors: Ghosh, Avipsa, Lecomte, Morgan, Kim‐Lee, Shin‐Ho, Radosevich, Alexander T.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 25.02.2019
• Edition: International ed. in English
• Subjects: Catalysis; Chlorides; Deoxygenation; organocatalysis; Perfluoroalkyl & polyfluoroalkyl substances; Phosphine; Phosphine oxide; phosphorus; reaction mechanisms; redox chemistry; Redox properties; Substrates; sulfenylation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201813919

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. 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.