TMG-chitotriomycin, a potent and selective inhibitor of the B-N-acetylglucosarninidases that possesses an unique N,N,N-trimethyl-D-glucosamine (TMG) residue, is revised to be the TMG-B-(1 -> 4)-chitotriose instead of the originally proposed alpha-anomer via its total synthesis, for which a highly convergent approach was developed in which the sterically demanding (1 -> 4)-glycosidic linkages are efficiently constructed by the Au(I)-catalyzed glycosylation protocol with glycosyl o-hexynylbenzoates as donors.