Photoredox-Catalyzed Alkene Amination: C(sp²)–H/N–H Radical–Radical Cross Dehydrogenative Coupling

Direct alkene C–H/N–H cross dehydrogenative coupling is an infrequent, highly challenging transformation. Herein, a photoredox radical–radical cross-coupling reaction between ketene dithioacetal as a persistent alkene radical cation and azole nitrogen center radical (NCR) was developed. This direct alkene amination proceeded through a synergistic photoredox and cobalt catalysis, with only H2 evolution. The reaction showed excellent tolerance and highly regio- and stereospecific manner, expanding the scope of C(sp2)–N construction methods and radical cross-coupling modes.