具有分子内NH-糖苷键的二糖和三糖的合成：用于构象研究的具有柔性和刚性糖苷键的分子。

Synthesis of di- and tri-saccharides with intramolecular NH-glycosidic linkages: molecules with flexible and rigid glycosidic bonds for conformational studies.

作者信息

Goddat J, Grey A A, Hricovíni M, Grushcow J, Carver J P, Shah R N

机构信息

Department of Molecular and Medical Genetics, University of Toronto, Ontario, Canada.

出版信息

Carbohydr Res. 1994 Jan 15;252:159-70. doi: 10.1016/0008-6215(94)90013-2.

DOI:10.1016/0008-6215(94)90013-2

PMID:8137358

Abstract

Attempted dephthalimidation of the trisaccharide 1-O-acetyl-3,4-di-O-benzyl- 2,6-di-O-(3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranosyl )-alpha-D-mannopyranose (1) and its derivatives 2 and 3, as well as the disaccharide 1-O-acetyl-3,4,6-tri-O-benzyl-2-O-(3,4,6-tri-O-acetyl- 2-deoxy-2-phthalimido-beta-D-glucopyranosyl)-alpha-D-mannopyranose (13), with hydrazine hydrate in ethanol at 80 degrees C, produced the trisaccharide-6-O-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-beta-D- glucopyranosyl)-3,4-di-O-benzyl-beta-D-mannopyranose-3',4',6'-tri-O-a cet yl- beta-D-glucopyranose 1,2'-N:1',2-O-dianhydride (4) and 3,4,6-tri-O-benzyl-beta-D-mannopyranose 3',4',6'-tri-O-acetyl-beta-D-glucopyranose 1,2'-N:1',2-O-dianhydride (14), respectively, containing an intramolecular NH-glycosidic linkage. The conventional deblocking of compounds 4 and 14 gave the completely deblocked trisaccharide 6-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-beta-D-mannopyranose beta-D-glucopyranose 1,2'-N:1',2-O-dianhydride (6) and the disaccharide beta-D-mannopyranose beta-D-glucopyranose 1,2'-N:1',2-O-dianhydride (16), respectively, containing an intact intramolecular NH-glycosidic bond. The unusual intra NH-glycosyl character makes the linkage rigid, and therefore these compounds should not only be useful for NMR studies but also as substrates or inhibitors of GlcNAc-transferases.

摘要

在80℃下，将三糖1-O-乙酰基-3,4-二-O-苄基-2,6-二-O-(3,4,6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚氨基-β-D-吡喃葡萄糖基)-α-D-甘露吡喃糖(1)及其衍生物2和3，以及二糖1-O-乙酰基-3,4,6-三-O-苄基-2-O-(3,4,6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚氨基-β-D-吡喃葡萄糖基)-α-D-甘露吡喃糖(13)，与水合肼在乙醇中进行邻苯二甲酰亚氨基脱除反应，分别生成了含有分子内NH-糖苷键的三糖-6-O-(2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖基)-3,4-二-O-苄基-β-D-甘露吡喃糖-3',4',6'-三-O-乙酰基-β-D-吡喃葡萄糖1,2'-N:1',2-O-二酐(4)和3,4,6-三-O-苄基-β-D-甘露吡喃糖3',4',6'-三-O-乙酰基-β-D-吡喃葡萄糖1,2'-N:1',2-O-二酐(14)。化合物4和14的常规脱保护反应分别得到了完全脱保护的三糖6-O-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)-β-D-甘露吡喃糖β-D-吡喃葡萄糖1,2'-N:1',2-O-二酐(6)和二糖β-D-甘露吡喃糖β-D-吡喃葡萄糖1,2'-N:1',2-O-二酐(16)，它们均含有完整的分子内NH-糖苷键。这种不寻常的分子内NH-糖基特性使该键具有刚性，因此这些化合物不仅对核磁共振研究有用，而且还可作为N-乙酰葡糖胺转移酶的底物或抑制剂。