以糖三氯乙酰亚胺酯作为供体，未保护的或部分保护的糖苷作为受体，简便有效地合成α-(1→6)-连接的甘露糖二糖、三糖、四糖、六糖、八糖和十二糖，以及β-(1→6)-连接的葡萄糖二糖、三糖、四糖、六糖和八糖。

A facile and effective synthesis of alpha-(1-->6)-linked mannose di-, tri-, tetra-, hexa-, octa-, and dodecasaccharides, and beta-(1-->6)-linked glucose di-, tri-, tetra-, hexa-, and octasaccharides using sugar trichloroacetimidates as the donors and unprotected or partially protected glycosides as the acceptors.

作者信息

Zhu Y, Kong F

机构信息

Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Academia Sinica, Beijing, People's Republic of China.

出版信息

Carbohydr Res. 2001 May 8;332(1):1-21. doi: 10.1016/s0008-6215(01)00070-2.

DOI:10.1016/s0008-6215(01)00070-2

PMID:11403082

Abstract

Reaction of 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl trichloroimidate with allyl alpha-D-mannopyranoside in the presence of TMSOTf selectively gave allyl 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1-->6)-alpha-D-mannopyranoside through an orthoester intermediate. Benzoylation of 3, followed by deallylation, and then trichloroimidation afforded the disaccharide donor 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroimidate, while benzoylation of 3 followed by selective removal of acetyl groups yielded the disaccharide acceptor allyl alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranoside. Coupling of 5 with 6 gave the tetrasaccharide allyl 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->6)-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranoside, which were converted into the tetrasaccharide donor 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroimdate and the tetrasaccharide acceptor allyl alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranosyl-(1-->6)-2,3,4-tri-O-benzoyl-alpha-D-mannopyranoside, respectively, by the same strategies as used for conversion of 3 into 5 and 6. Condensation of 5 with 13 gave the hexasaccharide 14, while condensation of 12 with 13 gave the octasaccharide 17. Dodecasaccharide 21 was obtained by the coupling of 12 with the octasaccharide acceptor 20. Similar strategies were used for the syntheses of beta-(1-->6)-linked glucose di-, tri-, tetra-, hexa-, and octamers. Deprotection of the oligosaccharides in ammonia-saturated methanol yielded the free alpha-(1-->6)-linked mannosyl and beta-(1-->6)-linked glucosyl oligomers.

摘要

在三甲基甲磺酸三甲基硅酯（TMSOTf）存在下，2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基三氯亚氨酸酯与烯丙基α-D-甘露吡喃糖苷反应，通过原酸酯中间体选择性地生成烯丙基2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基-(1→6)-α-D-甘露吡喃糖苷。3进行苯甲酰化反应，接着进行脱烯丙基反应，然后进行三氯亚氨酸酯化反应，得到二糖供体2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基三氯亚氨酸酯，而3进行苯甲酰化反应后选择性地除去乙酰基，得到二糖受体烯丙基α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖苷。5与6偶联得到四糖烯丙基2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基-(1→6)-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖苷，通过与将3转化为5和6相同的策略，将其分别转化为四糖供体2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基三氯亚氨酸酯和四糖受体烯丙基α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖基-(1→6)-2,3,4-三-O-苯甲酰基-α-D-甘露吡喃糖苷。5与13缩合得到六糖十四糖，而12与13缩合得到八糖十七糖。十二糖二十一糖是通过12与八糖受体20偶联得到的。类似的策略用于合成β-(1→6)-连接的葡萄糖二聚体、三聚体、四聚体、六聚体和八聚体。在氨饱和甲醇中对寡糖进行脱保护，得到游离的α-(1→6)-连接的甘露糖基和β-(1→6)-连接的葡萄糖基寡聚物。