2,3-Anhydrosugars in glycoside bond synthesis. Application to alpha-D-galactofuranosides.

We report here the use of 2,3-anhydro-D-gulofuranosyl thioglycosides and glycosyl sulfoxides in the synthesis of alpha-D-galactofuranosidic bonds, which are present in a range of bacterial and fungal glycoconjugates. This two-step method involves a stereoselective glycosylation in which a 2,3-anhydro-alpha-D-gulofuranoside is obtained either as the sole or as the major product, followed by a regioselective opening of the epoxide ring using lithium benzylate in the presence of (-)-sparteine. In exploring the scope of the method, donors protected at O5 and O6 with an isopropylidene acetal, benzyl ethers, or benzoate esters were studied. Overall, the glycosyl sulfoxides provided the products in slightly higher yields and selectivity, with the best results being obtained with benzylated and benzoylated substrates. In the epoxide ring-opening reactions, the acetal- and ether-protected donors afforded poor to modest regioselectivity, whereas the benzoylated products gave good yields of the desired alpha-D-galactofuranosides. The benzoyl-protected species are, therefore, the donors of choice for these reactions. The utility of the approach was demonstrated through the synthesis of three alpha-D-galactofuranosyl-containing oligosaccharides.