Chiral Hydroxamic Ester-Enabled Asymmetric Catellani Reaction for the Synthesis of P -Stereogenic Phosphepine Oxides

Asymmetric palladium/norbornene (NBE) cooperative catalysis is a powerful platform for assembling complex molecules. However, achieving enantiocontrol remains a fundamental challenge in cascades where the stereodetermining step occurs strictly after NBE extrusion. We report a conceptually distinct palladium-catalyzed annulation enabled by an exogenous chiral hydroxamic ester. This ligand remains coordinated to the palladium center throughout the catalytic cycle, affording diverse seven-membered P -stereogenic phosphepine oxides in moderate to good yields and up to 92% ee.