Alkylcyanation of Unactivated Alkenes with Protic C(sp3)‐H Feedstocks via Radical‐Initiated Intramolecular Cyano Group Migration Enabled by Photoredox/Brønsted Base Dual Catalysis

Cyanofunctionalization of alkenes via radical‐initiated cyano migration was a straightforward pathway to access alkyl nitriles. Herein, By the synergistic merger of photoredox catalysis and Brønsted base catalysis, a mild protocol of alkylcyanation of unactivated alkenes with protic C(sp3)−H feedstocks via intramolecular 1,4‐cyano group migration was reported. This method was enabled in an atom‐, and step‐economy manner, delivering a series of γ‐cyanoester derivatives in moderate to excellent yields.