Copper‐Catalyzed Cross‐Coupling Interrupted by an Opportunistic Smiles Rearrangement: An Efficient Domino Approach to Dibenzoxazepinones

Unexpected Smiles! An unusual and highly regioselective synthesis of dibenzoxazepinones by a domino sequence assisted by an unexpected Smiles rearrangement is reported. The process is effective on electronically differentiated phenols and shows a high tolerance to variation in the benzamide substituents. A plausible path for the reaction, supported by preliminary mechanistic data, is offered.