Electrocatalytic Amide Synthesis: Mechanistic Pathways and Selectivity Control in C-N Coupling.

Abstract

Electrocatalytic amide synthesis provides a promising strategy to construct amide bonds from simple carbon- and nitrogen-containing feedstocks under mild conditions. In contrast to conventional amidation, this approach uses electrode potential to regulate substrate activation and C─N bond formation, thereby offering opportunities to reduce reagent consumption and improve process sustainability. However, selective amide formation remains difficult because the target pathway competes with substrate over-oxidation, over-reduction, and the formation of non-amide C─N products. In this Review, we summarize recent advances in the electrocatalytic synthesis of carboxamides from an amide-specific mechanistic perspective. The discussion is organized into anodic oxidative amidation, cathodic reductive amidation, and integrated full-cell electrosynthesis. Particular emphasis is placed on carbonyl-level carbon activation, nitrogen-intermediate generation, interfacial regulation, electrolyte mediation, and reactor configuration. Finally, key mechanistic and engineering challenges are identified to guide the further development of selective, scalable amide electrosynthesis.