Modular Photocatalytic Three‐Component Gem ‐Difluoroalkylative Pyridylation of Alkenes via Pyridylphosphonium Salts

The difunctionalization of alkenes enables the efficient and simultaneous construction of two chemical bonds. However, methods for the simultaneous introduction of both a pyridine ring and a difluoromethyl group into alkene molecules remain scarce. Here, we report a strategy for the gem ‐difluoroalkylative pyridylation of alkenes under mild conditions using pyridylphosphonium salts as pyridine unit donors. This reaction enables highly regioselective installation of a pyridine unit and a gem ‐difluoromethyl group across the C═C bond, featuring broad substrate scope and high functional group tolerance. Furthermore, this protocol can be extended to enable remote C(sp 3 )─H bond functionalization via a 1,5‐hydrogen atom transfer, providing a route for rapid construction of molecular complexity and late‐stage derivatization of complex fluorinated molecules.