Thiocarbamate‐directed Cp*Co(III)‐Catalyzed Olefinic C−H Amidation: Facile Access to Enamines with High (Z)‐Selectivity

Abstract A thiocarbamate‐directed Cp*Co(III)‐catalyzed C−H oxidative amidation of olefins is achieved to synthesize a series of enamines. The key feature of this protocol is the use of earth‐abundant cobalt as catalyst and thiocarbamate as directing group, which provides an efficient and simple manner to synthesize enamines in good yields with high ( Z )‐selectivity. This reaction proceeds smoothly under very mild conditions (rt and air), and a wide range of functionalized alkenes, as well as dioxazolones, were compatible with the standard reaction conditions.