Photoredox-Catalyzed N-Directed Regioselective Difluoroalkylation of Unactivated C(sp 3 )-H Bonds.

We report a redox-neutral, visible-light-mediated difluoroalkylation of unactivated C(sp 3 )-H bonds in amides via nitrogen-centered radicals triggered intramolecular hydrogen atom transfer. Notably, all types (tertiary, secondary, and primary) of γ-C(sp 3 )-H bonds displayed excellent reactivity. This methodology presents a facile route for the regioselective introduction of α,α-difluoroketone fragments into organic molecules. Moreover, the resulting gem -difluoroketones can be readily converted to structurally diverse difluoro-containing molecules, offering broad potential applications in medicinal chemistry and chemical biology.