Here we report a mild and general method for the trifluoromethylthiolation of aldehydes using N-trifluoromethylthiosaccharin as the CF3S radical source and sodium decatungstate (NaDT) as the photocatalyst. This reaction proceeds via hydrogen atom abstraction by photoactivated DT and features good functional groups and substrate tolerance. Generally, electron-rich aldehydes demonstrate better reactivity than electron-deficient ones and good selectivity is observed for the trifluoromethylthiolation of aldehydic C–H bonds over tertiary and benzylic C–H bonds. Preliminary mechanistic studies have shown that a free radical process is involved.

A photocatalytic Smiles rearrangement, triggered by radical difluoromethylation of conjugated arylsulfonylated amides, was developed to construct both β-difluoromethyl amide and heterocyclic scaffolds selectively. This transformation features mild conditions and broad...

Photoredox-catalyzed addition of the difluororadical to unactivated alkenes has been found to trigger neophyl-like aryl and heteroaryl migrations which allowed the construction of a diverse series of difluoromethyl ketones.

This report describes the site-selective α-functionalization of sulfonylamide derivatives through the in-situ generation of imine intermediates. The NÀ F sulfonylamides, which could facilitate the elimination to generate imines, are coupled with TBACN to efficiently and mildly afford αamino cyanides. Comparing with Strecker reaction, this transformation offers a complementary strategy to efficiently construct α-amino cyanides from direct α CÀ H functionalization of sulfonylamindes. The reaction is also characterized by broad substrate scope and flash chromatography column free workup. More importantly, the new two-electron pathway to generate imines through manipulation of the leaving group allows us to achieve excellent α site-selectivity.