The Preferred Conformations of Glycosylalditols

Crystal structure analysis shows 6‐ O ‐(α‐D‐glucopyranosyl)‐D‐glucitol (isomaltitol 1 ) to have a bent glucitol chain linked to glucose in normal 4 C 1 ‐chair form, the middle section forming a planar zigzag chain that extends into the pyranoid ring. Comparative assessment of the conformational features of 1 , its D‐mannitol analogue 2 , and of some (1 → 4)‐linked analogues allows — in combination with Jeffrey's alditol rules and the exo ‐anomeric effect principles — to predict with significant confidence the preferred conformations of glycosylalditols in general.