A general photocatalytic hydrodefluorination and defluoroalkylation of electronically-variable ArCF3 by changing commercially-available arenethiolates

Abstract

Although defluorinative functionalization of trifluoromethylarenes has been studied by several research groups, different kinds of catalysts are required accordingly based on specific substrate families to obtain the corresponding RCF₂Ar compounds. Herein, we report a general photocatalytic approach for the selective hydrodefluorination (HDF) and defluoroalkylation (DFA) of ArCF₃. Using electronically-different arenethiolates as photosensitizers, 88 α,α-difluoromethyl compounds were synthesized from a broad range of electronically-variable trifluoromethylarenes, including natural products and bioactive molecules. Our mechanistic studies uncovered photo-induced electron donor–acceptor (EDA) complexation followed by silane-assisted C–F bond activation.