Methods for site-selective sulfamoylation of secondary hydroxyl groups in pyranosides are described. Using a boronic acid catalyst, selective installation of a Boc-protected sulfamoyl group at the equatorial position of cis-diols in manno- and galacto-configured substrates has been achieved. Activation of trans-diol groups in gluco- and galacto-configured substrates is also possible by employing an organotin catalyst.