Green Light-Driven Organophosphine-Catalyzed Iododifluoroalkylation of Alkynes

A green light-driven, organophosphine-catalyzed iododifluoroalkylation of alkynes using iododifluoroketones has been developed, eliminating the need for additional metal catalysts and bases. This protocol enables the efficient and sustainable synthesis of CF₂-derived alkenyl iodides under mild conditions, demonstrating excellent tolerance to iododifluoroketones, iododifluoroesters, and perfluoroalkyl iodides. Preliminary mechanistic studies suggest that the catalytic phosphine functions not only as a Lewis base, forming a charge-transfer complex with difluoroalkyl iodides through halogen-bonding interactions to generate R_f radicals, but also as a halogen transfer shuttle catalyst to facilitate the catalytic cycle.