Synthesis of Kdo-trisaccharide derivatives of chlamydial and enterobacterial LPS containing carboxyl-reduced or β-configurated Kdo-residues

Abstract

Five allyl glycosides corresponding to the 3-deoxy-D-manno-2-octulosonic acid (Kdo) containing genus-specific LPS epitope of Chlamydia were synthesized. Compounds 5 and 22 contain one carboxyl-reduced Kdo moiety linked to O-4 of the proximal Kdo unit, whereas the analogues 28, 34 and 36 each contain one β-linked Kdo-residue within the trisaccharide sequence Kdo p-(2→8)-Kdop-(2→4)-Kdop. Elaboration of the carboxyl-reduced derivatives was achieved by BF₃•Et₂O-catalyzed coupling of Kdo-fluoride derivatives 1 or 14 with the 7,8-O-carbonyl-derivative 2. The β-linked oligosaccharides were obtained by Helferich-glycosidation of the respective Kdo-disaccharide bromide derivatives 26 and 31. The deprotected compounds - characterized by H and ¹³C NMR spectroscopy - are suitable haptens for the immunochemical study of monoclonal antibodies directed against the Kdo-region of chlamydial and enterobacterial LPS.

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