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.