Aspinall G O, Khare N K, Sood R K, Chatterjee D, Rivoire B, Brennan P J
Department of Chemistry, York University, Toronto, Ontario, Canada.
Carbohydr Res. 1991 Sep 2;216:357-73. doi: 10.1016/0008-6215(92)84173-p.
The tetrasaccharide hapten released from the glycopeptidolipid (GPL) antigen of Mycobacterium avium serovar 20 has been characterized as O-(2-O-methyl-alpha-D-rhamnopyranosyl)-(1----3)-O-(2-O-methyl-alpha-L- fucopyranosyl)-(1----3)-alpha-L-rhamnopyranosyl-(1----2)-6-deoxy-L-talos e. Syntheses are reported of allyl glycosides of the outer disaccharide unit of this hapten, O-(2-O-methyl-alpha-D-rhamnopyranosyl)-(1----3)-2-O-methyl-alpha-L-fu copyranose , and also of the outer di- and tri-saccharide units of the GPL antigen of M. avium serovar 14, O-(N-formyl-alpha-L-kansosaminyl)-(1----3)-2-O-methyl-alpha-D-rham nopyranose and O-(N-formyl-alpha-L-kansosaminyl)-(1----3)-O-(2-O-methyl-alpha-D- rhamnopyranosyl)-(1----3)-2-O-methyl-alpha-L-fucopyranose. The key steps in the latter synthesis involve the preparation of allyl 4-azido-4,6-dideoxy-3-C-methyl-2-O-methyl-alpha-L-mannopyranoside as a precursor for the N-formylkansosamine unit, followed sequentially by conversion into and use of a trichloroacetimidate as glycosyl donor for di- and tri-saccharide formation, O-deacylation, reduction, and N-formylation. The allyl glycosides, representative of the haptens from both serovars, have been converted into neoglycoproteins (NGPs) and their serological activities have been compared in the light of the structural relationship between them.
从鸟分枝杆菌血清型20的糖肽脂（GPL）抗原中释放出的四糖半抗原已被鉴定为O-(2-O-甲基-α-D-吡喃鼠李糖基)-(1→3)-O-(2-O-甲基-α-L-吡喃岩藻糖基)-(1→3)-α-L-吡喃鼠李糖基-(1→2)-6-脱氧-L-塔罗糖。本文报道了该半抗原外二糖单元的烯丙基糖苷，即O-(2-O-甲基-α-D-吡喃鼠李糖基)-(1→3)-2-O-甲基-α-L-吡喃岩藻糖的合成，以及鸟分枝杆菌血清型14的GPL抗原外二糖和三糖单元，即O-(N-甲酰基-α-L-甘露糖胺基)-(1→3)-2-O-甲基-α-D-吡喃鼠李糖和O-(N-甲酰基-α-L-甘露糖胺基)-(1→3)-O-(2-O-甲基-α-D-吡喃鼠李糖基)-(1→3)-2-O-甲基-α-L-吡喃岩藻糖的合成。后一种合成的关键步骤包括制备烯丙基4-叠氮基-4,6-二脱氧-3-C-甲基-2-O-甲基-α-L-甘露吡喃糖苷作为N-甲酰基甘露糖胺单元的前体，随后依次转化为三氯乙酰亚胺酯并用作形成二糖和三糖的糖基供体、O-脱酰基、还原和N-甲酰化。代表两种血清型半抗原的烯丙基糖苷已被转化为新糖蛋白（NGP），并根据它们之间的结构关系比较了它们的血清学活性。
