Green Light‐Driven Organophosphine‐Catalyzed Iododifluoroalkylation of Alkynes

Abstract 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 CF 2 ‐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.