Cp*Co(III)-Catalyzed oxidative [5+2] annulation: regioselective synthesis of 2-aminobenzoxepines via C–H/O–H functionalization of 2-vinylphenols with ynamides

A Cp*Co(III)-catalyzed [5+2] C–H annulation reaction of 2-vinylphenols with ynamides was developed. The reaction led to the efficient synthesis of valuable 2-aminobenzoxepines in high regioselectivity. Mild reaction conditions, good functional group tolerance, and moderate to good yields were observed. The synthetic utility was demonstrated by a gram-scale synthesis and further transformations of the products. Preliminary mechanistic studies were conducted, and a possible catalytic cycle was proposed.