Synthesis towards thioglycoside donors commenced from commercial 1,2,3,4,6-penta-O-acetyl-b-D-glucose 1, undergoing thioglycosylation with EtSH using BF3×Et2O as a Lewis acid and affording the b-thiol in 87% yield (Scheme 1). Deacetylation using Na2CO3 in MeOH afforded tetrol 2 in 98% yield and an appropriate material to diversify the route to the required building blocks. Benzylidene protection using benzaldehyde dimethyl acetal with CSA in MeCN was followed by regioselective C3-O-benzylation using n Bu2SnO and CsF with benzyl bromide. Subsequent C2-O-benzoylation using BzCl and pyridine afforded thioglycoside 3 in 49% yield over three steps. From this material two divergent routes were progressed. The first saw regioselective reductive ring opening using BH3•THF and a catalytic amount of TMSOTf as Lewis acid to give a 6-OH,4-OBn protected material in 91% yield. COSY NMR correlation between a broad singlet at d = 1.97 ppm and H6 environments at d = 3.93 and 3.72 ppm indicated a C6-OH was present and the desired regiochemistry achieved. Reaction of this material with chloroacetyl chloride and pyridine afforded the desired donor 4 in 86% yield. Secondly, thioglycoside 3 was subjected to acidic benzylidene cleavage using CSA in MeOH at 40 °C, followed by regioselective C6-O-chloroacetylation at low temperature to afford alcohol 5 in 80% yield. Finally, C4-O-levulinoyl ester protection proceeded smoothly in 85% yield to generate glycosyl donor 6, alternatively protected at C4, compared to 4; the C4-O-Lev group enabling access to regioselective deprotection (versus C4 OBn in 4) and access to a glycosyl acceptor form. Furthermore, from tetrol 2 para-methoxyphenyl benzylidene protection was completed, followed by C2,C3-O-benzoylation to afford thioglycoside 7 in 88% yield over two steps. Reductive ring opening of PMP-benzylidene 7 was explored, for the first time, employing BH3•NMe3 complex and AlCl3. Initial yields in forming the desired C6-O-PMB regioisomer 8 were low (35-44%), noting amounts (22-30%) of returned 7 alongside an unwanted anomeric hydrolysis product formed during the 3 h reaction. By reducing the reaction time to 1 h (expedited by the addition of two equivalents of H2O), the isolated yield of 8 increased to 81% and was accessible on 10 g scale. Finally, C4-O-protection of 8 was completed using either TBDMSOTf or EDC/levulinic acid to afford orthogonally C4-protected donors 9 (91% yield) and 10 (77% yield), completing the panel.