The N-(1-deoxy- d-mannitol-1-yl) and N-(1-deoxy- d-glucitol-1-yl) derivatives of l-valine, l-alanine, l-threonine, and l-leucine were prepared by reductive amination of d-mannose and d-glucose with the appropriate amino acids, in the presence of sodium cyanoborohydride. N ε-(1-Deoxy- d-mannitol-1-yl)- and N ε-(1-deoxy- d-glucitol-1-yl)- l-lysine were prepared by similar reactions of hexoses with N α- tert-butoxycarbonyl and N α-benzyloxycarbonyl- l-lysine, followed by removal of the protecting groups. The structures were confirmed by 1H-n.m.r. spectroscopy, which showed that each compound was completely free of its C-2 epimer. The synthetic compounds may be used as reference compounds for the identification of N-(1-deoxyhexitol-1-yl)amino acids formed when N-(1-deoxy- d-fructose-1-yl) groups of nonenzymically glycosylated proteins, of the hemoglobin A 1c type, are reduced with sodium borohydride, and the protein is subjected to acid-catalyzed hydrolysis.