Iron‐Catalyzed <i>exo</i>‐Selective Synthesis of Cyanoalkyl Indolines via Cyanoisopropylarylation of Unactivated Alkenes

Abstract 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