与痢疾志贺氏菌1型O-特异性多糖相关的二糖至五糖的合成及其核磁共振研究。

Synthesis of di- to penta-saccharides related to the O-specific polysaccharide of Shigella dysenteriae type 1, and their nuclear magnetic resonance study.

作者信息

Pozsgay V, Coxon B, Yeh H

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

Bioorg Med Chem. 1993 Oct;1(4):237-57. doi: 10.1016/s0968-0896(00)82129-x.

DOI:10.1016/s0968-0896(00)82129-x

PMID:7521746

Abstract

The syntheses of oligosaccharide fragments of the O-specific polysaccharide of the lipopolysaccharide of Shigella dysenteriae type 1 are described, including disaccharides methyl O-alpha-D-mannopyranosyl-(1-->2)-alpha-D-galactopyranoside (1), and methyl O-(2-deoxy-2-propionamido-alpha-D-glucopyranosyl)-(1-->3)-alpha-L- rhamnopyranoside (2), trisaccharide methyl O-alpha-D-galactopyranosyl-(1-->3)-O-(2-acetamido-2-deoxy-alpha-D- glucopyranosyl)-(1-->3)-alpha-L-rhamnopyranoside (3), tetrasaccharide methyl O-alpha-L-rhamnopyranosyl-(1-->2)-O-alpha-D-galactopyranosyl-(1-->3)- O-(2-acetamido-2-deoxy-alpha-D-glucopyranosyl)-(1-->3)-alpha-L-rhamno -pyranoside (4), and pentasaccharide methyl O-alpha-L-rhamnopyranosyl-(1-->3)-O-alpha-L- rhamnopyranosyl-(1-->2)-O-alpha-D-galactopyranosyl- (1-->3)-O-(2-acetamido-2-deoxy-alpha-D-glucopyranosyl)-(1-->3)-alpha-L- rhamnopyranoside (5). The following monosaccharide building blocks were used as starting compounds: methyl 6-O-tert-butyldiphenylsilyl-3,4-O-isopropylidene-alpha-D-galact opy ranoside (8), methyl 3,4,6-tri-O-benzyl-2-O-(4-methoxybenzyl)-1-thio-beta-D- galactopyranoside (11), methyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-alpha- D-glucopyranoside (16), methyl 2-azido-4,6-O-benzylidene-2-deoxy-1-thio-alpha-D- glucopyranoside (18), methyl 2,4-di-O-benzyl-alpha-L-rhamnopyranoside (21), methyl 2,3,4-tri-O-benzoyl-1-thio-alpha-L-rhamnopyranoside (22), 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (23), and methyl 4-O-benzyl-alpha-L-rhamnopyranoside (24). Nuclear magnetic resonance data indicate that oligosaccharides 4 and 5 partially mimic the conformation of the O-specific polysaccharide of S. dys. type 1.

摘要

描述了痢疾志贺氏菌1型脂多糖O-特异性多糖寡糖片段的合成，包括二糖甲基O-α-D-甘露吡喃糖基-(1→2)-α-D-吡喃半乳糖苷（1）和甲基O-(2-脱氧-2-丙酰胺基-α-D-吡喃葡萄糖基)-(1→3)-α-L-鼠李吡喃糖苷（2）、三糖甲基O-α-D-吡喃半乳糖基-(1→3)-O-(2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基)-(1→3)-α-L-鼠李吡喃糖苷（3）、四糖甲基O-α-L-鼠李吡喃糖基-(1→2)-O-α-D-吡喃半乳糖基-(1→3)-O-(2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基)-(1→3)-α-L-鼠李吡喃糖苷（4）以及五糖甲基O-α-L-鼠李吡喃糖基-(1→3)-O-α-L-鼠李吡喃糖基-(1→2)-O-α-D-吡喃半乳糖基-(1→3)-O-(2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基)-(1→3)-α-L-鼠李吡喃糖苷（5）。使用了以下单糖构建块作为起始化合物：甲基6-O-叔丁基二苯基甲硅烷基-3,4-O-异亚丙基-α-D-吡喃半乳糖苷（8）、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（11）、甲基3,4,6-三-O-乙酰基-2-叠氮基-2-脱氧-1-硫代-α-D-吡喃葡萄糖苷（16）、甲基2-叠氮基-4,�-亚苄基-2-脱氧-1-硫代-α-D-吡喃葡萄糖苷（18）、甲基2,4-二-O-苄基-α-L-鼠李吡喃糖苷（21）、甲基2,3,4-三-O-苯甲酰基-1-硫代-α-L-鼠李吡喃糖苷（⒉）、2,3,4-三-O-苯甲酰基-α-L-鼠李吡喃糖基溴化物（23）以及甲基4-O-苄基-α-L-鼠李吡喃糖苷（24）。核磁共振数据表明，寡糖4和5部分模拟了痢疾志贺氏菌1型O-特异性多糖的构象。