Electrochemical synthesis and amidation of benzoin: benzamides from benzaldehydes

Abstract

Abstract The benzoin condensation starting from benzaldehyde and the subsequent benzoin amidation to benzamide can be efficiently carried out under very mild conditions in an electrolysis cell. Among the advantages of using electrochemistry to generate our active reagents, the use of the easily dosed and non pollutant electron, instead of stoichiometric amounts of redox reagents or bases, usually renders the electrochemical methodology “greener” than classical organic reactions. Benzoin is obtained in good yield (85 %) carrying out the reaction in the room temperature ionic liquid BMIm-BF4. In this electrochemical reaction this liquid salt assumes the double role of solvent-supporting electrolyte system and precatalyst, yielding the corresponding N-heterocyclic carbene. The subsequent benzoin amidation is carried out by electrochemically generated superoxide anion, in the presence of an aliphatic primary or secondary amine. In this case the system superoxide/molecular oxygen acts as base and oxidant, yielding very good yields of benzamides (up to 89 %).