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 Rf radicals, but also as a halogen transfer shuttle catalyst to facilitate the catalytic cycle.