Glucuronic acid-contg. di- and trisaccharide thioglycoside building blocks, Et (benzyl 2,3,4-tri-O-benzyl-b-D-glucopyranosyluronate)-(1 -> 2)-3- O-allyl-4,6-di-O-benzyl-1-thio-a-D-mannopyranoside, Et (benzyl 2,3,4-tri-O-benzyl-b-D-glucopyranosyluronate)-(1 -> 2)-6-O-acetyl-3-O-allyl-4-O-benzyl-1-thio-a-D-mannopyranoside and Et (2,3,4-tri-O-benzyl-b-D-xylopyranosyl)-(1 -> 4)-[(benzyl 2,3,4-tri-O-benzyl-b-D-glucopyranosyluronate)-(1 -> 2)]-3-O-allyl-6-O-benzyl-1-thio-a-D-mannopyranoside, corresponding to repetitive structures in the capsular polysaccharide (CPS) of Cryptococcus neoformans, have been synthesized. The blocks contain an orthogonal allyl group in the 3-position of the mannose residue to allow formation of the (1 -> 3)-linked mannan backbone of the CPS and benzyl ethers as persistent protecting groups to facilitate access to acetylated target structures. The glucuronic acid moiety was introduced using an acetylated trichloroacetimidate donor and the xylose residue employing the benzoylated bromo sugar to ensure b-selectivity in the couplings. Exchange to benzyl protecting groups was then performed at the di- or trisaccharide level. Assembly of suitable blocks employing DMTST as promoter in di-Et ether then afforded, in high yield and with stereoselectivity, a protected pentasaccharide corresponding to a C. neoformans serotype D CPS structure. [on SciFinder (R)]