methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside | 354986-45-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
• CAS: 354986-45-1
• 化学式: C₃₀H₃₃NO₆
• 分子量: 503.595
• InChiKey: GBPGWWXZBAMRRC-DVQUCECISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.47
• 重原子数：
  37.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  66.46
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside 在 盐酸 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 78.5h， 生成 methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3,6-di-O-benzyl-[2,3-di-O-benzyl-4,6-O-benzylidene-β-D-mannopyranosyl]-(1->4)-α-D-glucopyranoside
  参考文献：
  名称：

  Why Are the Hydroxy Groups of Partially Protected N-Acetylglucosamine Derivatives Such Poor Glycosyl Acceptors, and What Can Be Done about It? A Comparative Study of the Reactivity of N-Acetyl-, N-Phthalimido-, and 2-Azido-2-deoxy-glucosamine Derivatives in Glycosylation. 2-Picolinyl Ethers as Reactivity-Enhancing Replacements for Benzyl Ethers

  摘要：

  Competition experiments were used to determine that the 4-OH of a 2-deoxy-2-azidoglucose derivative is more reactive than that of the corresponding N-phthalimido glucose derivative which, in turn, is more easily glycosylated than the N-acetyl derivative. Glycosylation of the C-OH groups of the N,N-diacetyl and N-acetyl-N-benzyl glucosamine was also found to be superior to that of the simple N-acetyl substance. The 3-O-picolinyl ether of a 4,6-O-benzylidene-protected N-acetylglucosamine was shown to have a strong intramolecular hydrogen bond to the adjacent acetamide group. This interaction does not persist in the 3-O-picolinyl-6-O-benzyl N-acetylglucosamine derivative. owing to a probable competing hydrogen bond between the 4-OH and the picolinyl ether. However, in the 3-O-picolinyl-4-O-benzyl N-acetylglucosamine regioisomer the picolinyl-acetamide hydrogen bond persists and leads to an enhancement of reactivity of the 6-OH, over and above that in the corresponding 3-O-benzyl ether. due to disruption of the typical intermolecular amide hydrogen bonding scheme. It is demonstrated that the picolinyl ether is readily removed by hydrogenolysis at atmospheric pressure and room temperature.

  DOI：

  10.1021/ja010086b
• 作为产物：
  描述：

  溴甲苯 、 methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 以71%的产率得到methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Why Are the Hydroxy Groups of Partially Protected N-Acetylglucosamine Derivatives Such Poor Glycosyl Acceptors, and What Can Be Done about It? A Comparative Study of the Reactivity of N-Acetyl-, N-Phthalimido-, and 2-Azido-2-deoxy-glucosamine Derivatives in Glycosylation. 2-Picolinyl Ethers as Reactivity-Enhancing Replacements for Benzyl Ethers

  摘要：

  Competition experiments were used to determine that the 4-OH of a 2-deoxy-2-azidoglucose derivative is more reactive than that of the corresponding N-phthalimido glucose derivative which, in turn, is more easily glycosylated than the N-acetyl derivative. Glycosylation of the C-OH groups of the N,N-diacetyl and N-acetyl-N-benzyl glucosamine was also found to be superior to that of the simple N-acetyl substance. The 3-O-picolinyl ether of a 4,6-O-benzylidene-protected N-acetylglucosamine was shown to have a strong intramolecular hydrogen bond to the adjacent acetamide group. This interaction does not persist in the 3-O-picolinyl-6-O-benzyl N-acetylglucosamine derivative. owing to a probable competing hydrogen bond between the 4-OH and the picolinyl ether. However, in the 3-O-picolinyl-4-O-benzyl N-acetylglucosamine regioisomer the picolinyl-acetamide hydrogen bond persists and leads to an enhancement of reactivity of the 6-OH, over and above that in the corresponding 3-O-benzyl ether. due to disruption of the typical intermolecular amide hydrogen bonding scheme. It is demonstrated that the picolinyl ether is readily removed by hydrogenolysis at atmospheric pressure and room temperature.

  DOI：

  10.1021/ja010086b