Light‐Induced Divergent Cyanation of Alkynes Enabled by Phosphorus Radicals

Abstract A photochemically induced selective and divergent cyanation reaction of alkynes, enabled by phosphorus radicals, is described. With the use of simple triarylphosphine as a co‐catalyst, three cyanation reactions, including di‐hydrocyanation, anti‐ Markovnikov hydrocyanation, and domino hydrocyanation/reduction, can be divergently achieved, furnishing a wide array of alkyl dinitriles, alkenyl nitriles, and alkyl nitriles under mild conditions. Terminal and internal alkynes are applicable with high efficiency and excellent selectivity. Synthetic applications for biologically active agents and preliminary experimental and computational mechanistic studies are reported.