A Monte Carlo investigation of the conformational free energies of the aldohexopyranoses

Abstract

This paper is concerned with the estimation of the energy and free energy differences between the different aldohexopyranoses and between the two chair forms of each hexose. Methods have been developed to account for the deformation of the ring by steric effects between substituents. Calculated α : β ratios of the hexoses are in good agreement with experiment except for some cases in which the anomers have a large number of equatorial hydroxy groups. This effect is interpreted as evidence for an important hydration effect which results in a stabilization of anomers which fit particularly well into an ice-like lattice.