Electrochemical Reductive Fragmentation of Isocyanides: Toward Nonclassical Isocyanide-based Multicomponent Reactions

An electrochemical reductive fragmentation of isocyanides via β-scission of radical anions to generate alkyl radicals is reported, supported by cyclic voltammetry, EPR spectroscopy, radical trapping experiments and cyanide detection. Leveraging this pathway, a metal-free and mild nonclassical isocyanide-based multicomponent reaction was developed to afford diverse imide derivatives in up to 98% yield, and α-iminonitriles were accessible by removing the carboxylic acid component. Notably, trans-stilbene is suggested to act as a dual-function additive, serving as both a sacrificial reductant and a single electron transfer mediator in this transformation.