Zhu Yuliang, Chen Langqiu, Kong Fanzuo
Research Center for Eco-Environmental Sciences, Academia Sinica, PO Box 2871, 100085, Beijing, China.
Carbohydr Res. 2002 Feb 11;337(3):207-15. doi: 10.1016/s0008-6215(01)00307-x.
A highly concise and effective synthesis of the mannose octasaccharide of the N-linked glycan in the adhesion domain of human CD2 was achieved via TMSOTf-promoted selective 6-glycosylation of a trisaccharide 4,6-diol acceptor with a pentasaccharide donor, followed by deprotection. The pentasaccharide was constructed by selective 3,6-diglycosylation of 1,2-O-ethylidene-beta-D-mannopyranose with 2-O-acetyl-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate, while the trisaccharide was obtained by selective 3-O-glycosylation of allyl 4,6-O-benzylidene-alpha-D-mannopyranoside with the same disaccharide trichloroacetimidate, followed by debenzylidenation. The mannose hexasaccharide antigenic factor 13b was synthesized by condensation of a trisaccharide donor, 2-O-acetyl-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->3)-4,6-di-O-acetyl-2-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate, with a trisaccharide acceptor, methyl 3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranoside, followed by deprotection.
通过三甲基硅烷基三氟甲磺酸酯促进的三糖4,6 -二醇受体与五糖供体的选择性6 -糖基化反应，随后进行脱保护，实现了人CD2粘附结构域中N -连接聚糖的甘露糖八糖的高度简洁有效的合成。五糖是通过1,2 - O -亚乙基-β - D -甘露吡喃糖与2 - O -乙酰基-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基-(1→2)-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基三氯乙酰亚胺的选择性3,6 -二糖基化构建而成，而三糖是通过烯丙基4,6 - O -亚苄基-α - D -甘露吡喃糖苷与相同的二糖三氯乙酰亚胺的选择性3 - O -糖基化反应，随后进行脱亚苄基化反应得到的。甘露糖六糖抗原因子13b是通过三糖供体2 - O -乙酰基-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基-(1→2)-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基-(1→3)-4,6 -二-O -乙酰基-2 - O -苯甲酰基-α - D -甘露吡喃糖基三氯乙酰亚胺与三糖受体3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基-(1→2)-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖基-(1→2)-3,4,6 -三-O -苯甲酰基-α - D -甘露吡喃糖苷的缩合反应，随后进行脱保护反应合成的。
