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

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 sp³-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.