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Organophosphorus‐Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by P III /P V =O Redox Cycling
Author(s) -
Ghosh Avipsa,
Lecomte Morgan,
KimLee ShinHo,
Radosevich Alexander T.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201813919
Subject(s) - chemistry , electrophile , deoxygenation , sulfonyl , phosphine oxide , catalysis , phosphine , medicinal chemistry , trifluoromethyl , thiophene , electrophilic addition , oxidation state , substrate (aquarium) , functional group , ring (chemistry) , combinatorial chemistry , organic chemistry , alkyl , oceanography , polymer , geology
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.