痢疾志贺氏菌1型O-特异性多糖四糖和六糖片段的合成及二维核磁共振分析

Synthesis and two-dimensional nuclear magnetic resonance analysis of a tetra- and a hexa-saccharide fragment of the O-specific polysaccharide of Shigella dysenteriae type 1.

作者信息

Pozsgay V, Coxon B

机构信息

Laboratory of Developmental and Molecular Immunity, National Institute of Child Health and Human Development, National Institutes of Health, Bethesda, MD 20892.

出版信息

Carbohydr Res. 1994 May 5;257(2):189-215. doi: 10.1016/0008-6215(94)80035-9.

DOI:10.1016/0008-6215(94)80035-9

PMID:8013005

Abstract

The synthesis of the tetra- and hexa-saccharide methyl glycosides alpha-D-Galp-(1-->3)-alpha-D-GlcpNAc-(1-->3)-alpha-L-Rhap-(1-->3)- alpha-L-Rhap- OMe (1), and alpha-L-Rhap-(1-->3)-alpha-L-Rhap-(1-->2)-alpha-D-Galp-(1--> 3)-alpha-D-GlcpNAc- (1-->3)-alpha-L-Rhap-(1-->3)-alpha-L-Rhap-OMe (3) is described, which represent various epitopes of the O-specific polysaccharide of Shigella dysenteriae type 1. The following monosaccharide intermediates were used: 1,3-di-O-acetyl-2-O-benzoyl-4-O-benzyl-alpha-L-rhamnopyranose (6 alpha), methyl 2,4-di-O-benzyl-alpha-L-rhamnopyranoside (7), methyl 2,4-di-O-benzoyl-1-thio-alpha-L-rhamnopyranoside (8), 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (9), methyl 3,4,6-tri-O-benzyl-2-O-(4-methoxybenzyl)-1-thio-beta-D- galactopyranoside (13), methyl 2,3,4,6-tetra-O-benzyl-1-thio-beta-D- galactopyranoside (16), and 2-azido-4,6-O-benzylidene-3-O-bromoacetyl-2-deoxy-beta-D- glucopyranosyl chloride (19). A detailed analysis of the 1H and 13C NMR spectra of oligosaccharides 1 and 3 confirmed that the hexasaccharide 3 better approaches the conformation of the native polysaccharide, than either 1 or the homologous pentasaccharide 41.

摘要

描述了四糖和六糖甲基糖苷α-D-吡喃半乳糖-(1→3)-α-D-吡喃葡萄糖胺-(1→3)-α-L-吡喃鼠李糖-(1→3)-α-L-吡喃鼠李糖-OMe（1）和α-L-吡喃鼠李糖-(1→3)-α-L-吡喃鼠李糖-(1→2)-α-D-吡喃半乳糖-(1→3)-α-D-吡喃葡萄糖胺-(1→3)-α-L-吡喃鼠李糖-(1→3)-α-L-吡喃鼠李糖-OMe（3）的合成，它们代表痢疾志贺氏菌1型O-特异性多糖的各种表位。使用了以下单糖中间体：1,3-二-O-乙酰基-2-O-苯甲酰基-4-O-苄基-α-L-吡喃鼠李糖（6α）、甲基2,4-二-O-苄基-α-L-吡喃鼠李糖苷（7）、甲基2,4-二-O-苯甲酰基-1-硫代-α-L-吡喃鼠李糖苷（8）、2,3,4-三-O-苯甲酰基-α-L-吡喃鼠李糖基溴（9）、甲基3,4,6-三-O-苄基-2-O-（4-甲氧基苄基）-1-硫代-β-D-吡喃半乳糖苷（13）、甲基2,3,4,6-四-O-苄基-1-硫代-β-D-吡喃半乳糖苷（16）和2-叠氮基-4,6-O-亚苄基-3-O-溴乙酰基-2-脱氧-β-D-吡喃葡萄糖基氯（19）。对寡糖1和3的1H和13C NMR光谱的详细分析证实，六糖3比1或同源五糖41更接近天然多糖的构象。