phenyl 4,6-O-benzylidene-3-deoxy-3-phthalimido-2-O-(trimethylsilyl)-1-thio-α-D-mannopyranoside | 945631-71-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: phenyl 4,6-O-benzylidene-3-deoxy-3-phthalimido-2-O-(trimethylsilyl)-1-thio-α-D-mannopyranoside
• 英文别名: 2-[(2R,4aR,6R,7S,8S,8aS)-2-phenyl-6-phenylsulfanyl-7-trimethylsilyloxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl]isoindole-1,3-dione
• CAS: 945631-71-0
• 化学式: C₃₀H₃₁NO₆SSi
• 分子量: 561.731
• InChiKey: OJPIBXKGSZFOGO-JDYLRREKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  39
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  99.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-O-benzylidene-3-deoxy-3-phthalimido-2-O-(trimethylsilyl)-1-thio-α-D-mannopyranoside 、 1-金刚烷醇 在 二苯基亚砜 、 trifluoromethanesulfonic acid anhydride 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以77%的产率得到1-adamantanyl 4,6-O-benzylidene-3-deoxy-3-phthalimido-2-O-(trimethylsilyl)-α-D-mannopyranoside
  参考文献：
  名称：

  Direct Stereocontrolled Synthesis of 3-Amino-3-deoxy-β-Mannopyranosides:  Importance of the Nitrogen Protecting Group on Stereoselectivity

  摘要：

  The highly stereocontrolled synthesis of the 3-amino-3-deoxy-beta-mannopyranosides is achieved by means of thioglycoside donors protected with a 4,6-O-benzylidene or alkylidene acetal and a benzylidene imine group. Among the various nitrogen protecting groups investigated only the Schiff's base was found to give high beta-selectivity. N-Phthalimido and N-acetamido protected donors were found to be highly alpha-selective, whereas 3-azido-3-deoxy glycosyl donors gave intermediate selectivity. The reasons for the protecting group dependency are discussed in terms of the change in the O2-C2-C3-N3 torsional interaction on conversion of the covalent glycosyl triflates to the transient oxacarbenium ions.

  DOI：

  10.1021/jo070473p
• 作为产物：
  描述：

  在 吡啶 、 2,4,6-三甲基吡啶 、 盐酸 、 甲醇 、 高氯酸 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 36.5h， 生成 phenyl 4,6-O-benzylidene-3-deoxy-3-phthalimido-2-O-(trimethylsilyl)-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Direct Stereocontrolled Synthesis of 3-Amino-3-deoxy-β-Mannopyranosides:  Importance of the Nitrogen Protecting Group on Stereoselectivity

  摘要：

  The highly stereocontrolled synthesis of the 3-amino-3-deoxy-beta-mannopyranosides is achieved by means of thioglycoside donors protected with a 4,6-O-benzylidene or alkylidene acetal and a benzylidene imine group. Among the various nitrogen protecting groups investigated only the Schiff's base was found to give high beta-selectivity. N-Phthalimido and N-acetamido protected donors were found to be highly alpha-selective, whereas 3-azido-3-deoxy glycosyl donors gave intermediate selectivity. The reasons for the protecting group dependency are discussed in terms of the change in the O2-C2-C3-N3 torsional interaction on conversion of the covalent glycosyl triflates to the transient oxacarbenium ions.

  DOI：

  10.1021/jo070473p