An exceedingly simple, general, and stereoselective method for the preparation of ketomethylene dipeptide isosteres (5-(carbobenzyloxyamino)-2-alkyl-gamma-ketoesters) from Cbz-protected amino acids and scalemic 2-triflyloxy esters has been developed. The method is short (three steps), efficient, and highly diastereoselective and enantioselective. (C) 1997 Elsevier Science Ltd.