methyl 4,6-di-O-p-bromobenzyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside | 146195-55-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-di-O-p-bromobenzyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside
• CAS: 146195-55-3
• 化学式: C₂₈H₃₀Br₂O₈S
• 分子量: 686.415
• InChiKey: OWFDUZKDFYDZPL-QLHPUIKHSA-N

物化性质

• 沸点：
  749.6±60.0 °C(predicted)
• 密度：
  1.60±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  39.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  100.52
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  methyl 4,6-di-O-p-bromobenzyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside 在 sodium azide 、 四乙基氯化铵 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 96.33h， 生成 methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-α-D-altropyranoside
  参考文献：
  名称：

  Synthesis, crystalline structure, conformational analysis, and azidolysis of methyl 2,3-anhydro-α-d-manno- and -allo-pyranoside p-bromobenzyl

  摘要：

  Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-alpha-D-allopyranoside (6) was synthesized from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) via the intermediate methyl 4,6-di-O-p-bromobenzyl-2,3-di-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Treatment of 6 with sodium azide selectively afforded methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-alpha-D-glucopyranoside in 70% yield. Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-(17) and methyl 2,3-anhydro-4,6-di-O-benzyl-alpha-D-mannopyranoside (18) were obtained from 1 via the intermediates methyl 4,6-di-O-p-bromobenzyl- and methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Azidolysis of 17 and 18 with sodium azide in the presence of tetraethylammonium chloride in N,N-dimethylformamide gave the respective 3-azidoaltropyransides, in yields of 80%, by exclusive 3-attack. The crystal structure of compound 6 is orthorhombic with a space group of P2(1)2(1)2(1), and the 2,3-anhydropyranose moiety is in an almost ideal degrees-H-5 half-chair conformation. The crystals of 17 are also orthorhombic, belonging to space group P2(1)2(1)2(1), but the conformation is a hybrid of the degrees-H-5 half-chair and the degrees-E sofa. Analysis by NMR spectroscopy suggests that in solution in CDCl3 the conformation of 17 remains the same as, and that of 6 undergoes a change from, the respective solid-state conformations.

  DOI：

  10.1016/0008-6215(92)80086-g
• 作为产物：
  描述：

  methyl 2,3-di-O-allyl-4,6-di-O-p-bromobenzyl-α-D-glucopyranoside 在 sodium hydroxide 、 potassium tert-butylate 、 四丁基硫酸氢铵 、 溶剂黄146 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 13.0h， 生成 methyl 4,6-di-O-p-bromobenzyl-2-O-p-tolylsulfonyl-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis, crystalline structure, conformational analysis, and azidolysis of methyl 2,3-anhydro-α-d-manno- and -allo-pyranoside p-bromobenzyl

  摘要：

  Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-alpha-D-allopyranoside (6) was synthesized from methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) via the intermediate methyl 4,6-di-O-p-bromobenzyl-2,3-di-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Treatment of 6 with sodium azide selectively afforded methyl 3-azido-4,6-di-O-p-bromobenzyl-3-deoxy-alpha-D-glucopyranoside in 70% yield. Methyl 2,3-anhydro-4,6-di-O-p-bromobenzyl-(17) and methyl 2,3-anhydro-4,6-di-O-benzyl-alpha-D-mannopyranoside (18) were obtained from 1 via the intermediates methyl 4,6-di-O-p-bromobenzyl- and methyl 4,6-di-O-benzyl-2-O-p-tolylsulfonyl-alpha-D-glucopyranoside. Azidolysis of 17 and 18 with sodium azide in the presence of tetraethylammonium chloride in N,N-dimethylformamide gave the respective 3-azidoaltropyransides, in yields of 80%, by exclusive 3-attack. The crystal structure of compound 6 is orthorhombic with a space group of P2(1)2(1)2(1), and the 2,3-anhydropyranose moiety is in an almost ideal degrees-H-5 half-chair conformation. The crystals of 17 are also orthorhombic, belonging to space group P2(1)2(1)2(1), but the conformation is a hybrid of the degrees-H-5 half-chair and the degrees-E sofa. Analysis by NMR spectroscopy suggests that in solution in CDCl3 the conformation of 17 remains the same as, and that of 6 undergoes a change from, the respective solid-state conformations.

  DOI：

  10.1016/0008-6215(92)80086-g