3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate | 1310050-49-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate
• 英文别名: [(2R,3R,4R,5R,6R)-4-acetyloxy-5-azido-3-phenylmethoxy-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate
• CAS: 1310050-49-7
• 化学式: C₁₉H₂₁Cl₃N₄O₇
• 分子量: 523.757
• InChiKey: IGAYHWREEDCTGH-NQNKBUKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  119
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  甲基2,3,4-三-O-苯甲酰-α-D-吡喃葡萄糖苷 、 3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 [(2R,3R,4S,5R,6S)-2-[[(2R,3R,4R,5R,6R)-4-acetyloxy-6-(acetyloxymethyl)-3-azido-5-phenylmethoxyoxan-2-yl]oxymethyl]-4,5-dibenzoyloxy-6-methoxyoxan-3-yl] benzoate 、 [(2R,3R,4S,5R,6S)-2-[[(2S,3R,4R,5R,6R)-4-acetyloxy-6-(acetyloxymethyl)-3-azido-5-phenylmethoxyoxan-2-yl]oxymethyl]-4,5-dibenzoyloxy-6-methoxyoxan-3-yl] benzoate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157
• 作为产物：
  描述：

  (2S,4aR,7R,8R,8aR)-7-azido-2-phenyl-6-(p-tolylthio)hexahydropyrano[3,2-d][1,3]dioxin-8-ol 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 硼烷四氢呋喃络合物 、 三氟甲磺酸三甲基硅酯 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 6.5h， 生成 3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157