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.

Observing C–N bond formation in plasma: a case study of benzene and dinitrogen coupling via an arylnitrenium ion intermediate

“…Direct immobilization of molecular nitrogen into organic molecules has been advocated with the advantage of high atom economy, 7,8 and some important advances have been made regarding main group element bond formation, 9,10 among which C–N coupling is of particular interest. 11–13 The representative examples include, just to name a few, the coupling of arenes 14 and N 2 into silylated aniline derivatives under mediation by a transition metal complex, and the generation of N -containing molecules based on the pre-activated Li 2 CN 2 as a synthon. 15 It is noteworthy that in those above methods, the reactions that occurred under relatively harsh conditions involving potent reductants, and the scope of N 2 transformation is still very limited.…”