Electrocatalytic C−N Couplings at Cathode and Anode

Abstract Electrocatalytic C−N couplings are promising alternatives to construct C−N bonds and to synthesize vital chemicals, including amine, amide, amino acid, oxime, imine, and nitrile, under ambient conditions. In recent years, the electrocatalytic C−N coupling has attracted a wide range of research interest and has achieved considerable developments. Here, the electrocatalytic C−N coupling is systematically reviewed aiming at reductive cathode and oxidative anode. In the cathodic part, the electrocatalytic coupling reaction systems, the corresponding design principles of electrocatalysts for different reaction systems, the mechanism studies from experimental and theoretical aspects, and the application‐oriented electrocatalytic devices for electrocatalytic C−N couplings are summarized. Anodic C−N coupling offers a potential approach to replace the conventional energy‐demand synthesis protocols, and is an indispensable part of the green and controllable construction of unsaturated C = N and C≡N bonds. According to the principle that electron transfer is the crucial point in anodic C−N coupling, the anodic coupling reactions are sorted out based on the direct and the indirect C−N coupling paths, respectively. Finally, the challenges and outlooks in this field are proposed. Electrocatalytic C−N coupling is an appealing research topic in electrochemistry and possesses infinite possibilities in the future.