The identification of furanose and pyranose ring forms of the reducing units of oligosaccharides

Abstract

Several types of oligosaccharides with glucose, arabinose, or galactose units have been prepared by chemical degradation of oligosaccharides of known structures and by enzymatic syntheses utilizing macerans amylase or yeast galactosyltransferase and appropriate substrates and cosubstrates. The ring forms of reducing units of these oligosaccharides and of oligosaccharides composed of glucose and mannose have been identified by a combined method of analysis based on methylation, gas-liquid chromatography, and mass spectrometry. In the dimethyl sulfoxide solvent used for the methylations, the oligosaccharides with arabinose or galactose units at the reducing ends occur as arabinofuranose or galactofuranose ring forms to the extent of 55 and 65%, respectively. The remainder of these monosaccharide units are present in the pyranose ring form. Oligosaccharides with glucose or mannose units at the reducing ends occur primarily in the pyranose ring form. An interesting observation is the finding that the reducing units which carry substituents linked by α-glycosidic linkages occur in a higher percentage in the furanose ring forms than those which carry substituents linked by β-glycosidic linkages.