Highly Regio‐, Diastereo‐, and Enantioselective Synthesis of Tetrahydroazepines and Benzo[b]oxepines through Palladium‐Catalyzed [4+3] Cycloaddition Reactions

A novel Pd⁰ -catalyzed asymmetric [4+3] annulation reaction of two readily accessible starting materials has been developed for building seven-membered heterocyclic architectures. The potential [3+2] side pathway could be suppressed though fine tuning of the conditions. A broad scope of cycloaddition donors and acceptors participated in the transformation with excellent chemo-, regio-, diastereo-, and enantioselectivtities, leading to valuable tetrahydroazepines and benzo[b]oxepines.