Catalyst‐ and Reagent‐Free Electrochemical Azole C−H Amination

Catalyst‐ and chemical oxidant‐free electrochemical azole C−H aminations were accomplished via cross‐dehydrogenative C−H/N−H functionalization. The catalyst‐free electrochemical C−H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp 3 )−H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C−H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant.