Rhodium-catalyzed regio- and stereoselective β-C(sp2)-H amidation of enamines with dioxazolones to access vicinal diamines.

Herein, a Rh(III)-catalyzed regio- and stereoselective β-C(sp2)-H amidation of enamides with dioxazolones has been developed, which afforded a series of diverse vicinal diamines with high Z-selectivity. This protocol featured mild conditions, broad substrate scope, and functional-group compatibility. In addition, scale-up synthesis, related applications, and preliminary mechanistic explorations were also accomplished.