A new asymmetric transformation of amino acids was described. Thus, when N-salicylidene- D-alanyl-, D-phenylalanyl-, or D-phenylglycyl-L-isoleucinatocopper (II) was incubated at pH 8.5 and 80° C, the resulting mixture at equilibrium contained a complex of LL-dipeptide in the contents of 63–76%. The epimerization of dipeptides is based on the enhanced activity of N-terminal amino acids through complex formation.