ethyl 3-O-benzyl-4,6-O-benzylidene-2-O-(tert-butyldimethylsilyl)-1-deoxy-1-thio-α-D-mannopyranoside S-oxide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: ethyl 3-O-benzyl-4,6-O-benzylidene-2-O-(tert-butyldimethylsilyl)-1-deoxy-1-thio-α-D-mannopyranoside S-oxide
• 英文别名: [(4aR,6R,7S,8S,8aR)-6-ethylsulfinyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]oxy-tert-butyl-dimethylsilane
• 化学式: C₂₈H₄₀O₆SSi
• 分子量: 532.774
• InChiKey: QFCJCLIYIJNQAV-QULZUKKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.57
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  82.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzyl-4,6-O-benzylidene-2-O-(tert-butyldimethylsilyl)-1-deoxy-1-thio-α-D-mannopyranoside S-oxide 、 methyl 2,3,4-tri-O-acetyl-α-D-glucopyranose 在 三氟甲磺酸酐 、 2,6-di-tert-butyl-4-dimethylpyridine 作用下， 以 乙醚 为溶剂， 反应 4.5h， 以82%的产率得到methyl 2,3,4-tri-O-acetyl-6-O-<3-O-benzyl-4,6-O-benzylidene-2-O-(tert-butyldimethylsilyl)-β-D-mannopyranosyl>-(1->6)-α-D-glucopyranoside
  参考文献：
  名称：

  β-甘露糖吡喃糖苷和其他糖苷通过糖基三氟甲磺酸酯的直接化学合成

  摘要：

  提出了伯醇，仲醇和叔醇的β-甘露吡喃糖苷合成的高产率，高立体选择性的方法。在存在2,6-二叔丁基-4-甲基吡啶。这些三氟甲磺酸酯反应，然后小号Ñ 2样与醇得到的β型甘露糖苷。为了实现高选择性，需要使用4,6- O-亚苄基保护的甘露糖，以及使用O -2和O上的非参与性保护基团-3个捐助者。进一步证明，当耐受武装和解除武装的保护基团时，硫代糖苷/苯磺酰基三氟甲磺酸酯的活化适用于葡糖苷系列。

  DOI：

  10.1016/s0040-4020(98)00426-8
• 作为产物：
  描述：

  ethyl 4,6-O-benzylidene-1-thio-α-D-mannopyranoside 在 2,6-二甲基吡啶 、 二正丁基氧化锡 、 magnesium monoperoxyphthalate hexahydrate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 ethyl 3-O-benzyl-4,6-O-benzylidene-2-O-(tert-butyldimethylsilyl)-1-deoxy-1-thio-α-D-mannopyranoside S-oxide
  参考文献：
  名称：

  Chemistry of 1-Alkoxy-1-glycosyl Radicals:  The Manno- and Rhamnopyranosyl Series. Inversion of α- to β-Pyranosides and the Fragmentation of Anomeric Radicals

  摘要：

  The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.

  DOI：

  10.1021/jo951194h

文献信息

• Direct chemical synthesis of β-mannopyranosides and other glycosides via glycosyl triflates
  作者：David Crich、Sanxing Sun

  DOI：10.1016/s0040-4020(98)00426-8

  日期：1998.7

  High yield, highly stereoselective methods for the synthesis of β-mannopyranosides of primary, secondary, and tertiary alcohols are presented. Activation of mannosyl sulfoxides or mannosyl thioglycosides with trifluoromethanesulfonic anhydride or benzenesulfenyl triflate, respectively, leads to the efficient formation of α-mannosyl triflates at −78 °C in dichloromethane, in the presence of 2,6-di-

  提出了伯醇，仲醇和叔醇的β-甘露吡喃糖苷合成的高产率，高立体选择性的方法。在存在2,6-二叔丁基-4-甲基吡啶。这些三氟甲磺酸酯反应，然后小号Ñ 2样与醇得到的β型甘露糖苷。为了实现高选择性，需要使用4,6- O-亚苄基保护的甘露糖，以及使用O -2和O上的非参与性保护基团-3个捐助者。进一步证明，当耐受武装和解除武装的保护基团时，硫代糖苷/苯磺酰基三氟甲磺酸酯的活化适用于葡糖苷系列。
• Chemistry of 1-Alkoxy-1-glycosyl Radicals:  The Manno- and Rhamnopyranosyl Series. Inversion of α- to β-Pyranosides and the Fragmentation of Anomeric Radicals
  作者：David Crich、Sanxing Sun、Jarmila Brunckova

  DOI：10.1021/jo951194h

  日期：1996.1.1

  The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.