N‐Directed defluorinative γ‐C(sp3)−H allylation of sulfamate esters for synthesis of gem‐difluoroalkenes via photoredox catalysis

Abstract gem ‐Difluoroalkenes are unique structural motifs with important applications ranging from drugs to materials. Herein, we report a novel radical‐mediated defluorinative allylation of sulfamate esters with through distal C(sp 3 )−H functionalization under photoredox conditions. The reaction could readily incorporate various gem ‐difluoroalkene motifs into previously unfunctionalized sp 3 carbon centers. The transformation allows directly dual activation of N−H and C(sp 3 )−H bonds via a photocatalytic and redox‐neutral process, as well as using water as environmentally friendly co‐solvent. The reaction could provide a general and operationally simple method to access gem ‐difluoroalkene compounds with high diversity.