Selectively Charged and Zwitterionic Analogues of the Smallest Immunogenic Structure of Streptococcus Pneumoniae Type 14.

Zwitterionic polysaccharides (ZPs) have been shown in recent years to display peculiar immunological properties, thus attracting the interest of the carbohydrate research community. To fully elucidate the mechanisms underlying these properties and exploit the potential of this kind of structures, in depth studies are still required. In this context, the preparation of two cationic, an anionic, as well as two zwitterionic tetrasaccharide analogues of the smallest immunogenic structure of type 14 (SP14) capsular polysaccharide are presented.

Stereoselective synthesis of β-d-GlcNAc-(1→4)-D-Glc disaccharide starting from lactose.

The stereoselective preparation of the β-d-GlcNAc-(1→4)-D-Glc disaccharide starting from known 4-O-[6-O-(1-methoxy-1-methylethyl)-3,4-O-isopropylidene-β-d-talopyranosyl]-2,3:5,6-di-O-isopropylidene-aldehydo-D-glucose dimethyl acetal (2), in turn easily obtained from lactose, is reported. Key steps of this new procedure, that avoids the glycosylation reaction, are (a) a first epimerization at C-4' through an unusual procedure involving a completely stereospecific hydroboration-oxidation of the enol ether group of the hex-4-enopyranoside 4, obtained from 3 by base promoted acetone elimination, (b) an amination with inversion by S(N)2 reaction on an imidazylate intermediate, and, finally, (c) N-acetylation followed by complete deprotection.