Electrocatalyzed Cyanomethylation of Azomethines: A New Synthesis for β-Aminonitriles

Article abstract of DOI:10.1002/prac.19923340607

Certain Schiff-bases (2-7) react in acetonitrile (1) at a Hg-cathode in a new electrocatalyzed cyanomethylation method in good yields without sideproducts to β-aminonitriles (2a-7a).The synthesis is initiated by an electrochemical deprotonation of 1 by azomethine-radical anions in catalytical amount to acetonitril anions (B^-).During nucleophilic reaction of B^- with 2-7 up to its complete consumption, the cyanomethylation synthon B^- is regenerated in a cyclic, self-reproducing process.Quantum chemical calculation in context with cyanomethylation product analysis permit mechanistical insights and exact prediction of suitable azomethines and coupling position for B^-.