Divergent Generation of the Difluoroalkyl Radical and Difluorocarbene via Selective Cleavage of C-S Bonds of the Sulfox-CF 2 SO 2 Ph Reagent.

A new difluoroalkylation reagent Sulfox-CF 2 SO 2 Ph bearing both sulfoximine and sulfone moieties was prepared from commercially available SulfoxFluor and PhSO 2 CF 2 H. On one hand, the Sulfox-CF 2 SO 2 Ph reagent could act as a (phenylsulfonyl)difluoromethyl radical source under photoredox catalysis, in which the arylsulfoximidoyl group is selectively removed. On the other hand, under basic conditions, Sulfox-CF 2 SO 2 Ph could serve as a difluorocarbene precursor for S- and O-difluoromethylations with S- and O-nucleophiles, respectively, in which the phenylsulfonyl group in Sulfox-CF 2 SO 2 Ph is selectively removed (followed by α-elimination of the arylsulfoximidoyl group).