Moving forward, the secondary alcohol was transformed into the corresponding TBS ether using TBSOTf/2,6-lutidine (Scheme 6). We and others have established that activated oxathiazinane heterocycles are excellent synthons for ring-opening with a variety of nucleophiles. Accordingly, a Cbz group was appended to oxathiazinane 11 using benzyl chloroformate and TMEDA, and ring opening was effected by heating 12 with KOAc in DMSO to form linear intermediate 13. Many biologically active natural products contain carbamoylated hexose components. Thus, in our D-galactosamine synthons, we planned that one of the OH protecting groups would be a carbamate. Accordingly, the acetate of 13 was hydrolyzed using K2CO3 in MeOH, and alcohol 14 was converted into benzyl carbamate 15 by heating with benzyl isocyanate in toluene. Dihydroxylation of 15 proceeded smoothly with 10 mol% K2OsO4•2H2O and stoichiometric NMO. Cleavage with NaIO4 formed an aldehyde which was unstable to purification and thus was immediately subjected to hemiacetalization with TsOH. Based on the coupling constant of the anomeric proton (~2 Hz), we conclude that cyclization selectively furnished the alpha anomer. The free alcohols of pyranose 17 were converted into their benzoate esters using benzoyl chloride and TMEDA. The anomeric benzoate could be selectively deprotected using MeNH2 in THF. Overall, 17, 18, and 19 represent new Dgalactosamine synthons.