methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3,6-di-O-benzyl-α-D-glucopyranoside | 354986-46-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3,6-di-O-benzyl-α-D-glucopyranoside
• 英文别名: N-benzyl-N-[(2S,3R,4R,5S,6R)-5-hydroxy-2-methoxy-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]acetamide
• CAS: 354986-46-2
• 化学式: C₃₀H₃₅NO₆
• 分子量: 505.611
• InChiKey: YYJWASINTWIAPV-WYQCABFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3-di-O-benzyl-4,6-O-benzylidene-α-D-mannopyranosyl triflate 、 methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3,6-di-O-benzyl-α-D-glucopyranoside 在 丁二酸酐 、 三乙胺 、 magnesium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 76.5h， 以73 mg的产率得到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：

  methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 盐酸 、 sodium hydride 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 methyl N-acetyl-N-benzyl-2-amino-2-deoxy-3,6-di-O-benzyl-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

文献信息

• Why Are the Hydroxy Groups of Partially Protected <i>N</i>-Acetylglucosamine Derivatives Such Poor Glycosyl Acceptors, and What Can Be Done about It? A Comparative Study of the Reactivity of <i>N</i>-Acetyl-, <i>N</i>-Phthalimido-, and 2-Azido-2-deoxy-glucosamine Derivatives in Glycosylation. 2-Picolinyl Ethers as Reactivity-Enhancing Replacements for Benzyl Ethers
  作者：David Crich、Vadim Dudkin

  DOI：10.1021/ja010086b

  日期：2001.7.1

  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.