Iron‐Catalyzed exo‐Selective Synthesis of Cyanoalkyl Indolines via Cyanoisopropylarylation of Unactivated Alkenes

An iron‐catalyzed cyanoalkylation using azobisisobutyronitrile (AIBN) is reported. With unactivated double bond as the radical acceptor, N‐allyl anilines underwent cyanoisopropylation/cyclization cascade to afford 3‐cyanoalkyl indolines bearing a tertiary nitrile moiety, which were otherwise unavailable. Excellent exo‐selectivity was always observed, and such a selectivity and the unusual performance of the iron catalyst might be related to the metal bridging between the radical and the substrate. magnified image