Electrochemically Driven C4-Selective Decyanoalkylation of Cyanopyridines with Unactivated Alkyl Bromides Enabling C(sp 3 )-C(sp 2 ) Coupling.

With cyanopyridines and alkyl bromides as coupling partners, an electrochemically driven C4-selective decyanoalkylation has been established to access diverse 4-alkylpyridines in one step. The reaction proceeds through the single electron reduction/radical-radical coupling tandem process under mild electrolytic conditions, achieving the cleavage of the C(sp 2 )-CN bond and the formation of C(sp 3 )-C(sp 2 ). The practicality of this protocol is illustrated by no sacrificial anodes, a broad substrate scope, and gram-scale synthesis.