ChemInform Abstract: Arabinofuranosyl Oligosaccharides from Mycobacteria: Synthesis and Effect of Glycosylation on Ring Conformation and Hydroxymethyl Group Rotamer Populations.

Abstract

A series of α-d-arabinofuranosyl oligosaccharides (2−8) that are fragments of the arabinan portions of two polysaccharides present in the cell wall of Mycobacterium tuberculosis have been synthesized. Preparation of the oligosaccharides involved the sequential addition of arabinofuranosyl residues from thioglycoside donors to methyl glycoside acceptors. High-resolution NMR studies on the final products provided all 3JH,H values, which were in turn used in PSEUROT 6.2 calculations to determine both the identity and equilibrium populations of preferred conformers for each furanose ring in these glycans. Comparison of the ring conformers present in 2−8 with those available in the parent monosaccharide, methyl α-d-arabinofuranose (16), allowed the determination of the effect of glycosylation upon ring conformation. At equilibrium, 16 exists as an approximately equimolar mixture of OT4 (North, N) and 2T3 (South, S) conformers. These studies showed that glycosylation of 16 at OH5 resulted in no significant chan...