Chemodivergent Oxidative Annulation of Benzamides and Enynes via 1,4-Rhodium Migration

Chemodivergent annulative couplings have been realized between N-methoxy benzamides and 1,3-enynes via Rh-catalyzed C–H activation and 1,4-Rh migration. Under Rh/copper catalyzed aerobic conditions, the nitrogen annulation occurred as the major pathway. The chemoselectivity was switched to the oxygen annulation under proper condition control with stoichiometric amounts of Cu­(II) oxidant and NaOAc. Both coupling systems proceeded with a broad scope and functional group tolerance.