An Iridium‐Catalyzed Conia‐ene Reaction for the Diastereo‐ and Enantioselective Synthesis of Complex Ring Systems

Abstract Iridium‐catalyzed Conia‐ene reactions of α‐amino amides are described. These units undergo 6‐ or 7‐ exo cyclization onto amido‐tethered alkenes to provide benzofused N ‐heterocycles. In this process, challenging contiguous stereocenters are installed with high diastereo‐ and enantioselectivity. The method provides a versatile platform for constructing sp 3 ‐rich heterocycles, and offers unusual examples of alkenes engaging in enantio‐ and diastereoselective Conia‐ene reactions. This study adds to an emerging body of processes that exploit the directed generation of Ir‐enolates.