Photocatalytic Functionalization of Perfluoroalkyl Alkenyl Iodides via Vinyl Radicals: Synthesis of Perfluoroalkylated Naphthalenes

A photocatalytic [4 + 2] cycloaddition of perfluoroalkyl alkenyl iodides with 1,1-di(hetero)aryl alkenes was developed for the modular synthesis of multisubstituted naphthalenes. Through a key perfluoroalkylated vinyl radical intermediate that undergoes a sequence of intermolecular addition, Mallory-type cyclization, and dehydrogenative aromatization, the method enables the precise incorporation of diverse perfluoroalkyl moieties onto carbocycles. Interestingly, perfluoroalkyl alkenyl iodides exhibit distinct radical reactivity and selectivity features mainly originating from the structural and electronic attributes of the attached perfluoroalkyl group.