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.