Synthesis of trisaccharide determinants of enterobacterial common antigens

Article abstract of DOI:10.1016/0008-6215(86)80006-4

In the presence of silver silicate, the reaction of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-mannopyranosyl bromide with 1,6-anhydro-2-azido-3-O-benzyl-2-deoxy-beta-D-glucopyranose gave beta-glycosidically linked 1,6-anhydro-2-azido-3-O-benzyl-2-deoxy-4-O-(3,4,6- tri-O-acetyl-2-azido-2-deoxy-beta-D-mannopyranosyl)-beta-D- glucopyranose. After deacetylation and catalytic oxidation with oxygen and platinum, 1,6-anhydro-2-azido-4-O-[(2-azido-2-deoxy-beta-D-mannopyranosyl) uronic acid]-3-O-benzyl-2-deoxy-beta-D-glucopyranose was obtained. A series of intermediate steps led to the glycosyl donor 6-O-acetyl-2-azido-3-O-benzyl-4-O-[benzyl (3,4-di-O-acetyl-2-azido-2-deoxy-beta-D-mannopyranosyl)uronate]-2-deoxy- alpha, beta-glucopyranosyl chloride which was coupled with 8-methoxycarbonyloctyl 4-azido-2-O-benzyl-4,6-dideoxy-alpha-D-galactopyranoside to give 8-methoxycarbonyloctyl O-[benzyl (3,4-di-O-acetyl-2-azido-2-deoxy-beta-D-mannopyranosyl)uronate]- (1----4)-O-(6-O-acetyl-2-azido-3-O-benzyl-2-deoxy-alpha-D-glucopyranosyl )-(1----3)-4-azido-2-O-benzyl-4,6-dideoxy-alpha-D-galactopyranoside. Deblocking gave the spacer-linked repeating unit of the enterobacterial common antigen, beta-D-ManpNAcA-(1----4)-alpha-D-GlcpNAc-(1----3)-alpha- D-Fucp4NACO(CH2)8CO2CH3.