4-(2-trimethylsilanyl-ethoxymethoxy)-bicyclo[2.2.2]octan-2,6-dione | 1245907-36-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 4-(2-trimethylsilanyl-ethoxymethoxy)-bicyclo[2.2.2]octan-2,6-dione
• 英文别名: 4-(2-Trimethylsilylethoxymethoxy)bicyclo[2.2.2]octane-2,6-dione
• CAS: 1245907-36-1
• 化学式: C₁₄H₂₄O₄Si
• 分子量: 284.428
• InChiKey: JOWVFTWFDULJLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(2-trimethylsilanyl-ethoxymethoxy)-bicyclo[2.2.2]octan-2,6-dione 在 蔗糖 作用下， 以 乙醇 、 水 为溶剂， 反应 48.0h， 生成 (-)-(1R,4R,6S)-6-hydroxy-4-(2-trimethylsilanylethoxymethoxy)-bicyclo[2.2.2]octan-2-one 、 (1S,4S,6R)-6-hydroxy-4-(2-trimethylsilanylethoxymethoxy)-bicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  Asymmetric baker’s yeast reductions of bridgehead-substituted bicyclo[2.2.2]octane-2,6-dione derivatives followed by conversion into catalytically active BODOLs for the diethylzinc addition to benzaldehyde

  摘要：

  4-Substituted bicyclo[2.2.2]octane-2,6-diones have been synthesized and tested as substrates in the enantioselective reduction with baker's yeast to give the corresponding hydroxy ketones. It was found that the derivative bearing a TIPSO group at the 4-position was not reduced at all while that with a TBDMSO group gave 87% yield and 46% ee. Other 4-oxy functionalized derivatives were reduced with varying yields (36-87%) and ees (10-82%). The best result was obtained for the 4-Oallyl derivative (80% yield, 82% ee). The hydroxy ketones carrying the benzyloxy and allyloxy groups at the 4-position were converted into the corresponding BODOLs, which were tested as catalysts in the diethylzinc addition to benzaldehyde. In this reaction the ees were 90% and 89%, respectively, which showed that BODOLs substituted at the 4-position are essentially as good catalysts in this reaction as those bearing a hydrogen. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.06.003
• 作为产物：
  描述：

  4-(2-trimethylsilanyl-ethoxymethoxy)-bicyclo[2.2.2]oct-5-en-2-one 在 dimethyl sulfide borane 、 水 、 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 12.0h， 以42%的产率得到4-(2-trimethylsilanyl-ethoxymethoxy)-bicyclo[2.2.2]octan-2,6-dione
  参考文献：
  名称：

  Asymmetric baker’s yeast reductions of bridgehead-substituted bicyclo[2.2.2]octane-2,6-dione derivatives followed by conversion into catalytically active BODOLs for the diethylzinc addition to benzaldehyde

  摘要：

  4-Substituted bicyclo[2.2.2]octane-2,6-diones have been synthesized and tested as substrates in the enantioselective reduction with baker's yeast to give the corresponding hydroxy ketones. It was found that the derivative bearing a TIPSO group at the 4-position was not reduced at all while that with a TBDMSO group gave 87% yield and 46% ee. Other 4-oxy functionalized derivatives were reduced with varying yields (36-87%) and ees (10-82%). The best result was obtained for the 4-Oallyl derivative (80% yield, 82% ee). The hydroxy ketones carrying the benzyloxy and allyloxy groups at the 4-position were converted into the corresponding BODOLs, which were tested as catalysts in the diethylzinc addition to benzaldehyde. In this reaction the ees were 90% and 89%, respectively, which showed that BODOLs substituted at the 4-position are essentially as good catalysts in this reaction as those bearing a hydrogen. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.06.003