[与HNK-1抗原相关的寡糖的合成。2. 3'''-O-(3-O-磺基-β-D-葡萄糖醛酸吡喃糖基)-乳糖-N-新四糖β-丙基糖苷的合成]

[Synthesis of oligosaccharides related to HNK-1 antigen. 2. Synthesis of 3'''-O-(3-O-sulfo-beta-D-glucuronopyranosyl)-lacto-N-neotetrao se beta-propylglycoside].

作者信息

Kononov L O, Kornilov A V, Sherman A A, Zyrianov E V, Zatonskiĭ G V, Shashkov A S, Nifant'ev N E

机构信息

Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia.

出版信息

Bioorg Khim. 1998 Aug;24(8):608-22.

PMID:9784880

Abstract

A derivative of allyl 3"-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-beta-lactoside with a free OH group at C-4GlcNAc was glycosylated with trichloroacetimidate of selectively protected GlcA(beta 1-->3)Gal alpha disaccharide in dichloromethane in the presence of trimethylsilyl triflate resulting in a pentasaccharide product with an 82% yield. This product was converted to monohydroxy derivative with a free OH group at C-3GlcA via the formation and the subsequent opening of the 6,3-lactone ring in the glucuronic acid residue. The 3"'-O-sulfation of the monohydroxy derivative, the removal of the protective groups, and the reduction of the allyl aglycon yielded the pentasaccharide propyl glycoside NaSO3-3GlcA(beta 1-->3)Gal(beta 1-->4)GlcNAc(beta 1-->3)Gal(beta 1-->4)Glc beta-Opr comprising the oligosaccharide chain of the SGGL-1 glycolipid, which is recognized by HNK-1 antibodies. NaSO3-3GlcA(beta 1--> 3)Gal beta OAll, GlcA(beta 1-->3)Gal(beta 1-->4)GlcNAc(beta 1-->3)Gal(beta 1-->4)Glc beta-OPr and GlcA(beta 1-->3)Gal beta OAll were synthesized in a similar way.

摘要

在三氟甲磺酸三甲基硅酯存在下，将具有C-4GlcNAc游离羟基的烯丙基3''-O-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)-β-乳糖苷衍生物与选择性保护的GlcA(β1→3)Galα二糖的三氯乙酰亚胺酯在二氯甲烷中进行糖基化反应，得到产率为82%的五糖产物。通过葡糖醛酸残基中6,3-内酯环的形成及随后的开环，该产物转化为在C-3GlcA处具有游离羟基的单羟基衍生物。单羟基衍生物的3'''-O-硫酸化、保护基团的去除以及烯丙基苷元的还原，得到了包含SGGL-1糖脂寡糖链的五糖丙基糖苷NaSO3-3GlcA(β1→3)Gal(β1→4)GlcNAc(β1→3)Gal(β1→4)Glcβ-Opr，其可被HNK-1抗体识别。NaSO3-3GlcA(β1→3)GalβOAll、GlcA(β1→3)Gal(β1→4)GlcNAc(β1→3)Gal(β1→4)Glcβ-OPr和GlcA(β1→3)GalβOAll以类似方式合成。