NMR characterization of α- and β-mannopyranurono-2,6-lactones

Abstract

Determining the stereochemistry at the anomeric position of glycosides is imperative in chemical synthesis. As for 1,2-cis-β-glycosides such as β-mannosides, 13C-1H coupling constants, 1JCHs, are conventionally used when glycosides are in an ordinary chair conformation. In this work, we searched for appropriate criteria to determine the stereochemistry of products in a recently developed glycosylation reaction using 2,6-lactones. As a result, we found that α-glycosides exhibited vicinal coupling constants of around 3.0 Hz at the anomeric proton, as well as a long-range coupling between protons at C-1 and C-5, whereas β-glycosides had coupling constants of 1.2 Hz at most. These figures are expected to be useful for future assignments. In addition, the observations obtained from this study revealed the conformation of glycosides with a 2,6-lactone moiety.