Electrochemically Initiated Hydrocyanomethylation of N‐Heteroaryl‐Substituted Azomethines

The acetonitrile anion ( 1 ‐), generated by electrochemical initiation and chemical regeneration, may be used as cyanomethylation reagent for C,N double bond structures, e.g. for hydrocyanomethylation of π‐deficient N‐heteroaryl‐substituted Schiff bases ( 2–12 ) yielding the β‐aminonitriles ( 2a–12a ). The synthesis is initiated by deprotonation of acetonitrile ( 1 ) to 1 − by cathodically generated azomethine radical anions ( 2 −· –12 −· ) followed by nucleophilic reaction of 1 − with 2–12 up to its complete consumption, in a cyclic self‐reproducing process of 1 − . Besides 2a–12a , 3,4‐heteroaryl‐substituted 4‐amino‐3‐butenonitriles and 1,3‐heteroaryl‐substituted 1,3‐diaminoisobutyronitiles are formed in the course of a nearly currentless reaction.