Enantioselective Formal [4 + 3] Annulations to Access Benzodiazepinones and Benzoxazepinones via NHC/Ir/Urea Catalysis

A robust and scalable formal [4 + 3] annulation reaction for the synthesis of optically pure 1,4-benzodiazepinones and 1,4-benzoxazepinones has been established by a combined catalytic system consisting of a chiral NHC, a chiral Ir/phosphine-olefin complex, and an achiral urea, enabling the asymmetric synthesis of a selective inhibitor of mitochondrial F1F0 ATP hydrolase.