Synthesis and NMR spectroscopic investigation of oligosaccharides containing Kdo and l- glycero- d- manno-heptopyranosyl residues

• Published in: Carbohydrate research 1993-05, Vol.243 (2), p.273-291
• Main Authors: Hofinger, Andreas, Kosma, Paul, Christian, Rudolf, Bock, Klaus, Brade, Helmut
• Format: Article
• Language: English
• Subjects: Carbohydrate Conformation; Carbohydrate Sequence; Disaccharides - chemical synthesis; Disaccharides - chemistry; Heptoses; Indicators and Reagents; Lipopolysaccharides - chemistry; Magnetic Resonance Spectroscopy - methods; Molecular Sequence Data; Oligosaccharides - chemistry; Optical Rotation; Sugar Acids; Trisaccharides - chemical synthesis; Trisaccharides - chemistry
• ISSN: 0008-6215; 1873-426X
• DOI: 10.1016/0008-6215(93)87033-O

The disaccharides O-(sodium 3-deoxy-α- d- manno-2-octulopyranosylonate)-(2 → 8)-sodium (allyl 3- deoxy-β- d- manno-2-octulopyranosid)onate ( 8), O- l- glycero-α- d- manno-heptopyranosyl-(1 → 7)-sodium (allyl 3-deoxy-β- d- manno-2-octulopyranosid)onate ( 12), and O-α- d-mannopyranosyl-(1 → 7)-sodium (allyl 3-deoxy-β- d- manno-2-octulopyranosid)onate ( 21) and the branched trisaccharides O- l- glycero-α- d- manno-heptopyranosyl-(1 → 7)-[ O-(sodium 3-deoxy-α- and -β- d- manno-2-octulopyranosylonate)-(2 → 8)]-sodium (allyl 3-deoxy-β- d- manno-2-octulopyranosid)onate ( 15 and 16) and O-α- d-mannopyranosyl- (1 → 7)-[ O-(sodium 3-deoxy-α- d- manno-2-octulopyranosylonate)-(2 → 8)]-sodium (allyl 3-deoxy-β- d- manno-2-octulopyranosid)onate ( 24) were prepared. Per- O-acetylated mannopyranosyl or Kdo bromide derivatives were employed for the glycosylation steps under helferich conditions, whereas the imidate derivative 9 was used for the coupling of the l- glycero- d- manno-heptopyranosyl residues. The oligosaccharides were fully characterized by NMR spectroscopic data. Their structures correspond to an artificial linkage pattern providing a potential cross-reactive epitope for antibodies directed against the inner-core-region of enterobacterial as well as chlamydial lipopolysaccharides.