The assignment of carbonyl resonances in 13C-n.m.r. spectra of peracetylated mono- and oligo-saccharides containing D-glucose and D-mannose: an alternative method for structural determination of complex carbohydrates.

In the present study, proton homonuclear (COSY) and 13C-1H heteronuclear shift-correlation, n.m.r. spectroscopies have been used to assign the carbonyl carbon resonances of peracetylated D-gluco- and D-mannopyranose monosaccharides and oligosaccharides containing residues of parent D-glucopyranose monomers. Chemical shifts of these assigned resonances, particularly those arising from acetyl groups near to aglycon substitution sites, were found to be sensitive to the position and configuration of glycosidic linkages present. In addition, evidence is presented that indicates that the shifts of these carbonyl carbon resonances depend on long-range interactions with other peracetylated pyranose monomers resulting from folding of the oligosaccharide chain. These results suggest that carbonyl carbon resonances of peracetylated carbohydrates may be useful probes of oligosaccharide structure.