Electronically Directed Convergent Electrochemical <i>meta</i>‐C─H Alkylation of Pyridine

Abstract Substituted pyridine is a valuable building block for the meta ‐C─H alkylation of pyridine, which has been less developed than the established ortho‐ and para‐alkylation protocols. In this work, we report electrochemical meta ‐C─H alkylation reactions using 4‐cyano‐pyridine as the template. Triggered by single‐electron reduction, the anionic radical of 4‐cyano‐pyridine is amenable to nucleophilic attack and radical cross coupling. With these properties, meta ‐C─H primary/secondary/tertiary alkylations of pyridine are achieved. The product 3‐alkyl‐4‐CN‐pyridine can serve as an entry for multiple functionalizations of polysubstituted pyridines.