鸟分枝杆菌-胞内分枝杆菌-瘰疬分枝杆菌血清复合物中血清型9和25糖肽脂抗原相关抗原决定簇的四糖合成

Synthesis of tetrasaccharides related to the antigenic determinants from the glycopeptidolipid antigens of serovars 9 and 25 in the Mycobacterium avium-M. intracellulare-M. scrofulaceum serocomplex.

作者信息

Takeo K, Aspinall G O, Brennan P J, Chatterjee D

出版信息

Carbohydr Res. 1986 Aug 1;150:133-50. doi: 10.1016/0008-6215(86)80011-8.

Abstract

The synthesis of the tetrasaccharides O-(2,3-di-O-methyl-alpha-L-fucopyranosyl)-(1----4)-O-(2,3- di-O-methyl-alpha-L-fucopyranosyl)-(1----3)-O-alpha-L-rhamnopyranosyl -(1----2)-6-deoxyl-L-talose (36) and O-(2-O-methyl-alpha-L-fucopyranosyl)-(1----4)-O-(2-O-methyl-alpha-L- fucopyranosyl)-(1----3)-O-alpha-L-rhamnopyranosyl-(1----2)-6-deoxy-L- talose (41) is described. The former and the latter structures, respectively, have been proposed as the carbohydrate chains in the polar glycopeptidolipid antigens of serovars 9 and 25 in the Mycobacterium avium-M. intracellulare-M. scrofulaceum serocomplex. Glycosylation of allyl 2,3-di-O-methyl-alpha-L-fucopyranoside with 4-O-benzoyl-2,3-di-O-methyl-alpha-L-fucopyranosyl chloride gave the alpha-linked disaccharide derivative, which was O-deallylated and converted into the corresponding disaccharide alpha-chloride. This was coupled with benzyl 3,4-di-O-benzyl-6-deoxy-2-O-(2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)- alpha-L-talopyranoside (32) to give a fully protected tetrasaccharide derivative, which was deprotected to furnish 36. Likewise, 3-O-benzyl-4-O-(3,4-di-O-acetyl-2-O-methyl-alpha-L- fucopyranosyl)-2-O-methyl-alpha-L-fucopyranosyl chloride, prepared by way of condensation of allyl 3-O-benzoyl-2-O-methyl-alpha-L-fucopyranoside with 2-O-methyl-3,4-di-O-(p-nitrobenzoyl)-alpha-L-fucopyranosyl bromide, reacted with 32, to provide, after removal of blocking groups, 41.

摘要

本文描述了四糖O-(2,3-二-O-甲基-α-L-呋喃岩藻糖基)-(1→4)-O-(2,3-二-O-甲基-α-L-呋喃岩藻糖基)-(1→3)-O-α-L-鼠李吡喃糖基-(1→2)-6-脱氧-L-塔罗糖（36）和O-(2-O-甲基-α-L-呋喃岩藻糖基)-(1→4)-O-(2-O-甲基-α-L-呋喃岩藻糖基)-(1→3)-O-α-L-鼠李吡喃糖基-(1→2)-6-脱氧-L-塔罗糖（41）的合成。前者和后者的结构分别被认为是鸟分枝杆菌-胞内分枝杆菌-瘰疬分枝杆菌血清复合物中血清型9和25的极性糖肽脂抗原中的碳水化合物链。烯丙基2,3-二-O-甲基-α-L-呋喃岩藻糖苷与4-O-苯甲酰基-2,3-二-O-甲基-α-L-呋喃岩藻糖基氯进行糖基化反应，得到α-连接的二糖衍生物，该衍生物进行O-脱烯丙基化反应并转化为相应的二糖α-氯代物。将其与苄基3,4-二-O-苄基-6-脱氧-2-O-(2,4-二-O-苯甲酰基-α-L-鼠李吡喃糖基)-α-L-塔罗吡喃糖苷（32）偶联，得到一个完全保护的四糖衍生物，脱保护后得到36。同样，通过烯丙基3-O-苯甲酰基-2-O-甲基-α-L-呋喃岩藻糖苷与2-O-甲基-3,4-二-O-(对硝基苯甲酰基)-α-L-呋喃岩藻糖基溴缩合制备的3-O-苄基-4-O-(3,4-二-O-乙酰基-2-O-甲基-α-L-呋喃岩藻糖基)-2-O-甲基-α-L-呋喃岩藻糖基氯与32反应，在去除保护基后得到41。