衣原体属特异性脂多糖表位四糖的合成。

Synthesis of a tetrasaccharide of the genus-specific lipopolysaccharide epitope of Chlamydia.

作者信息

Kosma P, Bahnmüller R, Schulz G, Brade H

机构信息

Institut für Chemie, Universität für Bodenkultur Wien, Vienna, Austria.

出版信息

Carbohydr Res. 1990 Dec 15;208:37-50. doi: 10.1016/0008-6215(90)80083-f.

DOI:10.1016/0008-6215(90)80083-f

PMID:1707757

Abstract

Allyl 2-acetamido-2-deoxy-3,4-O-(1,1,3,3-tetraisopropyldisiloxan-1,3- diyl)-beta-D- glucopyranoside was coupled with methyl (4,5,7,8-tetra-O-acetyl-3-deoxy-alpha-D-manno-2-octulopyranosyl bromide)onate (1) to give a good yield of the alpha-(2----6)-linked disaccharide, isolated after deacetylation and regioselective conversion into the corresponding 7',8'-O-carbonyl or 7',8'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) derivatives, respectively. Subsequent glycosylation with 1 gave a high yield of the alpha- and beta-(2"----4')-linked trisaccharide derivatives 16 and 18, whereas block synthesis using the alpha-(2----8)-linked Kdo-disaccharide bromide derivative 19 afforded a low yield of the corresponding alpha- and beta-(2"----4')-linked tetrasaccharide derivatives 20 and 22. Removal of the protecting groups furnished the disaccharide allyl O-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----6)-2-acetamido -2-deoxy- beta-D-glucopyranoside, the trisaccharide allyl O-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----4)-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----6)-2-acetamido -2-deoxy- beta-D-glucopyranoside, and the tetrasaccharide allyl O-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----8)-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----4)-(sodium 3-deoxy-alpha-D-manno-2-octulopyranosylonate)-(2----6)-2-acetamido -2-deoxy- beta-D-glucopyranoside in high yield. Copolymerization of the allyl glycosides with acrylamide gave artificial polyvalent haptens suitable for defining epitope specificities of monoclonal antibodies directed against Chlamydia lipopolysaccharides.

摘要

烯丙基 2-乙酰氨基-2-脱氧-3,4-O-(1,1,3,3-四异丙基二硅氧烷-1,3-二亚基)-β-D-吡喃葡萄糖苷与甲基(4,5,7,8-四-O-乙酰基-3-脱氧-α-D-甘露-2-辛酮糖基溴)酸酯(1)偶联，以良好的产率得到α-(2→6)连接的二糖，经脱乙酰化并分别区域选择性转化为相应的 7',8'-O-羰基或 7',8'-O-(1,1,3,3-四异丙基二硅氧烷-1,3-二亚基)衍生物后分离得到。随后用 1 进行糖基化反应，以高收率得到α-和β-(2''→4')连接的三糖衍生物 16 和 18，而使用α-(2→8)连接的 Kdo-二糖溴化物衍生物 19 进行片段合成，得到相应的α-和β-(2''→4')连接的四糖衍生物 20 和 22 的产率较低。脱去保护基后，高产率地得到二糖烯丙基 O-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→6)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷、三糖烯丙基 O-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→4)-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→6)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷和四糖烯丙基 O-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→8)-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→4)-(3-脱氧-α-D-甘露-2-辛酮糖酸钠)-(2→6)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷。烯丙基糖苷与丙烯酰胺的共聚反应得到了适用于确定针对衣原体脂多糖的单克隆抗体表位特异性的人工多价半抗原。