The linkage of S-phenyl 2,3-di-O-benzyl-alpha-D-thiomannopyranoside to a cross-linked polystyrene support in the form of its 4,6-O-polystyrylborinate ester is described. The activation of this polymer-supported mannosyl donor is achieved at -60 degreesC in dichloromethane in the presence of 2,4,6-tri-tert-butylpyrimidine with the combination 1-benzenesulfinyl piperidine and trifluoromethanesulfonic anhydride. Addition of the donor alcohol at -60 degreesC followed by warming to room temperature and subsequent cleavage from the resin by gentle heating in aqueous acetone yields anomerically pure 2,3-di-O-abenZyl-beta-D-mannopyranosides in excellent yield, Successful, diastereoselective coupling is demonstrated with a range of primary, secondary, and tertiary glycosyl acceptors, including typical carbohydrates and threonine derivatives.