Cyanide as an Efficient and Mild Catalyst in the Aminolysis of Esters

Article abstract of DOI:10.1021/jo00386a025

Cyanide anion was found to be a versatile catalyst in the aminolysis of nonactivated esters.A comparative study on various catalysts, including (dimethylamino)pyridine, 2-hydroxypyridine, imidazole, and sodium cyanide, in the ammonolysis of ethyl (S)-1-ethyl-2-pyrrolidinecarboxylate (1) in methanol showed sodium cyanide to be the superior catalyst.Furthermore, the reaction was completely stereoconservative; i.e., less than 1percent racemization occurred.Cyanide ion also proved to be an efficient catalyst in the transesterification with the solvent.Comparative studies on 1, ethyl benzoate (4), ethyl 3-phenylpropionate (5), and ethyl phenoxyacetate (6) in aminolysis with ammonia, methylamine, and dimethylamine in methanol showed cyanide to be a general catalyst.The reactivity order for various esters was found to be MeNH2 > NH3 > Me2NH.