The reactivity of perbenzoylated thioglycosides with various thiol aglycons has been compared and quantified using competitive glycosylation expts. Me 2,3,4-tri-O-benzyl-a-D-glucopyranoside was employed as acceptor and DMTST as a promoter. The reactivity was found, as expected, to depend on the electron donating properties of the aglycon. Hence, the most reactive donor, the cyclohexyl thioglycoside, was found to be about three times as reactive as the thioethyl glycoside, which in turn was twice as reactive as the thiomethyl donor. The thiophenyl donor was even less reactive, whereas p-halophenyl donors were inert under the glycosylation conditions used - but could be activated using NIS-TfOH as promoter. Furthermore, it was found that galactosyl donors were three to four times more reactive than the corresponding glucosyl deriv. These results allowed the design of an orthogonal coupling between thioglycosides with the same protecting groups (benzoyls) but with different thiol aglycons. [on SciFinder (R)]