Computational study of the conformational space of methyl 2,4-diacetyl-beta-D-xylopyranoside: 4C1 and 1C4 chairs, skew-boats (2SO, 1S3), and B3,O boat forms

Ring and substituent rotamer conformations of methyl 2,4-diacetyl-beta-D-xylopyranoside, for which experimental results are controversial, were studied in the gas phase and in solvents of different polarity (CCl4, CHCl3, DMSO, and H2O) by B3LYP density functional theory. The 1C4 chair is the most stable ring form in the gas phase, followed by 4C1 and 2S0. Solvents of increasing polarity shift the equilibrium toward the 4C1 chair. Homodesmotic reaction energies show that the 1C4 and 2SO forms are stabilized by hydrogen bonding and anomeric effects and that steric repulsion is smallest in the 4C1 chair and largest in skew-boats.