Electrochemical Behavior of Selected Imine Derivatives, Reductive Carboxylation, α‐Amino Acid Synthesis

The electrochemical behavior of six selected imine derivatives, where , phenyl, phenyl; phenyl, phenyl, phenyl; H, isobutyl, phenyl; H, phenyl, benzyl; phenyl, phenyl, benzyl; and H, isobutyl, benzyl, has been investigated in acetonitrile/0.1M tetraethylammonium perchlorate and liquid ammonia/0.1 M potassium iodide. In anhydrous media the radical anion species are highly reactive, yielding mostly polymeric and dimeric products with some saturated amine formation. Addition of weak proton donors leads to an increased yield of the saturated amine. If the reduction is carried out in the presence of a high yield of α‐amino acid is observed, but only if the imine is directly reducible. The reaction imines reducing at less negative potentials than that for the direct reduction of give high current efficiencies, while low current efficiencies characterize the reduction of imines whose potentials are approximately equal to or more negative than that for . Mechanistic aspects of the reaction are discussed.