The synthesis of derivs. of (thioglucopyranosid)uronates, e.g. I (R = Bn, Ac, Bz), with different ester groups (acetate, benzoyl, pivaloyl, and anisoyl) at O-2 is described. The synthesis proceeds via a two-step oxidn. (DMSO/DCC followed by PDC/MeOH) of C-6 on a suitably protected glucose deriv. to give directly the Me glucuronic ester without affecting the thioglycoside. The thioglucuronides were tested as donors in coupling reactions with unreactive carbohydrate alcs. using dimethyl(methylthio)sulfonium triflate (DMTST) as promoter. Due to the activating benzyl protecting groups at O-3 and -4, the sluggishness of fully acylated glucuronic acid donors could be overcome and glucuronide disaccharides were produced in fair to good yields. The glucuronides were obtained with the desired b-configuration because of the participating group at O-2. Among the different ester groups tried, the benzoyl group was found to give the highest yield in the couplings. [on SciFinder (R)]