Electrocatalytic Minisci Acylation Reaction of N-Heteroarenes Mediated by NH4I

An electrochemical C-H acylation of electron-deficient N-heteroarenes with α-keto acids is reported. This first electrochemical Minisci acylation reaction proceeded using NH₄I as a redox catalyst. A broad N-heteroarene scope and high functional group tolerance are observed. Selective monoacylation of N-heteroarenes is achieved via control of acyl radical at a low concentration. The results of cyclic voltammetry and control experiments disclose that the electrogenerated I₂ is likely the active species to initiate the oxidative decarboxylation of carboxylate anion via an acyl hypoiodite intermediate. The electrochemical Minisci acylation provides a straightforward approach for the late-stage functionalization of pharmacophores.