The trimethylsilyl group on the 6-position of methyl 2,3,4,6-tetra-O-trimethylsilyl-α-D-glucopyranoside is preferentially removed by methanolysis, using basic or acidic catalysts, giving methyl 2,3,4-tri-O-trimethylsilyl-α-D-glucopyranoside in high yield (>80%). Reaction of the latter with acetic anhydride, benzoyl chloride, or phenyl isocyanate produces the corresponding 6-substituted derivatives in quantitative yield. The trimethylsilyl residues from the latter compounds are hydrolyzed by 50% aqueous methanol with the concomitant formation of 6-O-acetyl, 6-O-benzoyl, or 6-carbanilate derivatives of methyl α-D-glucopyranoside in excellent yield. Chemical and proton magnetic resonance (p.m.r.) studies established the structure of methyl 2,3,4-tri-O-trimethylsilyl-α-D-glucopyranoside, and of subsequent derivatives prepared from this compound. Infrared and p.m.r. evidence is offered to support conclusions regarding the conformation of the groups or atoms attached to C6 and C5 of the glucoside residue in some of these compounds.