Substitutional and solvation effects on conformational equilibria. Effects on the interaction between opposing axial oxygen atoms

Abstract

Evidence based both on nuclear magnetic resonance and rotation data primarily obtained from methyl 3-deoxy-β-L-erythro-pentopyranoside and a number of its derivatives is interpreted to show that the electrostatic repulsion between the oxygen atoms at the 2 and 4 positions is substantially less when these oxygens are linked to acyl groups than when in the form of either methyl ethers or as hydroxyl groups hydrogen bonded to solvent. Also, experimental evidence is presented which requires the hydrogen bridge between two axially disposed hydroxyl groups to be substantially strengthened by hydrogen bonding of the free hydroxyl by solvent.