methyl 6-azido-2,3-di-O-benzyl-6-deoxy-4-O-trimethylsilyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-azido-2,3-di-O-benzyl-6-deoxy-4-O-trimethylsilyl-α-D-glucopyranoside
• 英文别名: [(2R,3R,4R,5R,6S)-2-(azidomethyl)-6-methoxy-4,5-bis(phenylmethoxy)oxan-3-yl]oxy-trimethylsilane
• 化学式: C₂₄H₃₃N₃O₅Si
• 分子量: 471.629
• InChiKey: WFDRDANZAAGFSZ-SJSRKZJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.06
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  60.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 6-azido-2,3-di-O-benzyl-6-deoxy-4-O-trimethylsilyl-α-D-glucopyranoside 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 以95%的产率得到methyl 6-azido-2,3-di-O-benzyl-6-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Preparation of Primary and Secondary Azidosugars from Diols using the Dioxaphosphorane Methodology

  摘要：

  Treatment of methyl 2,3-di-O-benzyl-alpha-D-glucopyranoside (1), methyl 2,3-di-O-acetyl-alpha-D-glucopyranoside (4), 3-O-benzyl-1,2-O-(1-methylethylidene)-alpha-D-glucofuranose (6), 3-O-acetyl-1,2-O-(1-methylethylidene)-alpha-D-glucofuranose (9), 1,2-O-(1-methylethylidene)-alpha-D-xylofuranose (11) and methyl 2,3-di-O-acetyl-alpha-D-galactopyranoside (15) with diisopropylazodicarboxylate-triphenylphosphine in tetrahydrofuran led to the corresponding dioxaphosphoranes, which were opened by trimethylsilyl azide affording the silylated primary azidodeoxysugars. When the same reaction was performed on methyl 2,3-di-O-benzyl-alpha-D-galactopyranoside (20), an inversion of the regioselectivity of the dioxaphosphorane opening was observed, leading mainly to the 4-azido-4-deoxy-alpha-D-glucopyranoside derivative 27.

  DOI：

  10.1080/07328309908544029
• 作为产物：
  描述：

  叠氮基三甲基硅烷 、 2,3-二-o-苄基-alpha-d-吡喃葡萄糖苷甲酯 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 3.5h， 以89%的产率得到methyl 6-azido-2,3-di-O-benzyl-6-deoxy-4-O-trimethylsilyl-α-D-glucopyranoside
  参考文献：
  名称：

  Regioselective azidotrimethylsilylation of carbohydrates and applications thereof

  摘要：

  在Mitsunobu条件下，实现了碳水化合物（单糖和双糖）高产率的叠加三甲基硅烷化。碳水化合物的叠加在0 °C下仅在单醇、二醇和三醇的初级醇位点进行，保护/未保护的糖苷中，剩余的二级羟基则被硅烷化。令人惊讶的是，在所有碳水化合物底物中没有观测到二级羟基的叠加反应。该方法的应用已用于氨基糖、三唑和氮糖的合成。

  DOI：

  10.1039/c2ob26324f

文献信息

• Preparation of Primary and Secondary Azidosugars from Diols using the Dioxaphosphorane Methodology
  作者：Dominique Lafont、Paul Boullanger

  DOI：10.1080/07328309908544029

  日期：1999.1

  Treatment of methyl 2,3-di-O-benzyl-alpha-D-glucopyranoside (1), methyl 2,3-di-O-acetyl-alpha-D-glucopyranoside (4), 3-O-benzyl-1,2-O-(1-methylethylidene)-alpha-D-glucofuranose (6), 3-O-acetyl-1,2-O-(1-methylethylidene)-alpha-D-glucofuranose (9), 1,2-O-(1-methylethylidene)-alpha-D-xylofuranose (11) and methyl 2,3-di-O-acetyl-alpha-D-galactopyranoside (15) with diisopropylazodicarboxylate-triphenylphosphine in tetrahydrofuran led to the corresponding dioxaphosphoranes, which were opened by trimethylsilyl azide affording the silylated primary azidodeoxysugars. When the same reaction was performed on methyl 2,3-di-O-benzyl-alpha-D-galactopyranoside (20), an inversion of the regioselectivity of the dioxaphosphorane opening was observed, leading mainly to the 4-azido-4-deoxy-alpha-D-glucopyranoside derivative 27.
• Regioselective azidotrimethylsilylation of carbohydrates and applications thereof
  作者：Mallikharjuna Rao L、Syed Khalid Yousuf、Debaraj Mukherjee、Subhash Chandra Taneja

  DOI：10.1039/c2ob26324f

  日期：——

  Azidotrimethylsilylation of carbohydrates (monosaccharides and disaccharides) has been achieved in high yields under Mitsunobu conditions. The azidation of carbohydrates is effected at 0 °C essentially only at the primary alcoholic position in mono, di- and triols in protected/unprotected glycosides, whereas the remaining secondary hydroxyl groups got silylated. Surprisingly, no azidation of the secondary hydroxyls was observed in all the carbohydrate substrates. Applications of the methodology for the synthesis of amino sugars, triazoles and azasugars are reported.

  在Mitsunobu条件下，实现了碳水化合物（单糖和双糖）高产率的叠加三甲基硅烷化。碳水化合物的叠加在0 °C下仅在单醇、二醇和三醇的初级醇位点进行，保护/未保护的糖苷中，剩余的二级羟基则被硅烷化。令人惊讶的是，在所有碳水化合物底物中没有观测到二级羟基的叠加反应。该方法的应用已用于氨基糖、三唑和氮糖的合成。