phenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl-(1->4)-2-O-acetyl-3,6-di-O-benzyl-1-thio-β-D-glucopyranoside | 299174-92-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl-(1->4)-2-O-acetyl-3,6-di-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: Phenyl-2-O-acetyl-3,6-di-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside
• CAS: 299174-92-8
• 化学式: C₆₂H₆₄O₁₁S
• 分子量: 1017.25
• InChiKey: YADRMGJVYGNKFX-WWBLMGCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.32
• 重原子数：
  74.0
• 可旋转键数：
  25.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  109.37
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl-(1->4)-2-O-acetyl-3,6-di-O-benzyl-1-thio-β-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 以97%的产率得到phenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl-(1->4)-3,6-di-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Prearranged Glycosides, Part 10. Intramolecular Glycosylation with Cellobiosyl, Lactosyl, and Maltosyl Donors

  摘要：

  Acetyl protected 1,2-O-(1-methoxyethylidene)-disaccharides 1 of maltose, cellobiose, and Lactose, respectively were converted via the corresponding benzyl protected couterparts 2, the benzyl protected phenyl 2-O-acetyl-3 and 2-O-unprotected 1-thio-glycoside disaccharides 4 into 2-O-succinoylated disaccharides 5. The latter were esterified with benzyl 2-O-benzoyl-4,6-di-O-benzylidene-alpha-D-glucopyranoside (6) to afford succinyl linked derivatives 7 the benzylidene groups of which were regioselectively opened to give prearranged glycoside trisaccharides 8. Intramolecular glycosylation of the latter with N-iodosuccinimide resulted in exclusive formation of the corresponding alpha-(1-->)-linked trisaccharides 9. No influence of the donor moiety on the diastereoselectivity of the intramolecular glycosylation was observed.

  DOI：

  10.1080/07328300008544113
• 作为产物：
  描述：

  溴甲苯 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium hydride 、 mercury dibromide 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 5.0h， 生成 phenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl-(1->4)-2-O-acetyl-3,6-di-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Prearranged Glycosides, Part 10. Intramolecular Glycosylation with Cellobiosyl, Lactosyl, and Maltosyl Donors

  摘要：

  Acetyl protected 1,2-O-(1-methoxyethylidene)-disaccharides 1 of maltose, cellobiose, and Lactose, respectively were converted via the corresponding benzyl protected couterparts 2, the benzyl protected phenyl 2-O-acetyl-3 and 2-O-unprotected 1-thio-glycoside disaccharides 4 into 2-O-succinoylated disaccharides 5. The latter were esterified with benzyl 2-O-benzoyl-4,6-di-O-benzylidene-alpha-D-glucopyranoside (6) to afford succinyl linked derivatives 7 the benzylidene groups of which were regioselectively opened to give prearranged glycoside trisaccharides 8. Intramolecular glycosylation of the latter with N-iodosuccinimide resulted in exclusive formation of the corresponding alpha-(1-->)-linked trisaccharides 9. No influence of the donor moiety on the diastereoselectivity of the intramolecular glycosylation was observed.

  DOI：

  10.1080/07328300008544113

文献信息

• Chemoselective activation of ethyl <i>vs</i>. phenyl thioglycosides: one-pot synthesis of oligosaccharides
  作者：Cian Mc Carthy、Xiangming Zhu

  DOI：10.1039/d0ob01606c

  日期：——

  pattern. Both armed and disarmed thioglycosides exhibited high chemoselectivity towards the promoter system. Chemoselective glycosylation was subsequently applied to one-pot synthesis, thus providing an efficient means to oligosaccharides.

  乙基和苯基硫糖苷是碳水化合物化学中最常见的两种硫糖苷供体。然而，乙基与苯基硫苷的化学选择性活化在文献中非常罕见。在这项工作中，乙基硫苷可以很容易地用N-三氟甲基硫糖精/TMSOTf 系统在具有相同或什至更多武装保护基模式的苯基硫苷存在下被活化。武装和解除武装的硫糖苷对启动子系统都表现出高化学选择性。随后将化学选择性糖基化应用于一锅法合成，从而为寡糖提供了一种有效的方法。