4-(tert-butyldimethylsilanyloxy)bicyclo[2.2.2]octane-2,6-dione | 868673-73-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(tert-butyldimethylsilanyloxy)bicyclo[2.2.2]octane-2,6-dione
• 英文别名: 4-[Tert-butyl(dimethyl)silyl]oxybicyclo[2.2.2]octane-2,6-dione
• CAS: 868673-73-8
• 化学式: C₁₄H₂₄O₃Si
• 分子量: 268.428
• InChiKey: GMWGIGGRKXOTST-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(tert-butyldimethylsilanyloxy)bicyclo[2.2.2]octane-2,6-dione 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 0.67h， 以50%的产率得到4-hydroxybicyclo[2.2.2]octane-2,6-dione
  参考文献：
  名称：

  桥头羟基双环[2.2.2]辛烷衍生物的合成1

  摘要：

  描述了从1，3-环己二酮开始，向4-羟基双环[2.2.2]辛烷-2，6-二酮衍生物3的两个独立的合成路线。

  DOI：

  10.1021/jo051284e
• 作为产物：
  描述：

  (+/-)-endo/exo-4-(tert-butyldimethylsilanyloxy)-6-hydroxybicyclo[2.2.2]octan-2-one 在 potassium permanganate 、 copper(II) sulfate 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以90%的产率得到4-(tert-butyldimethylsilanyloxy)bicyclo[2.2.2]octane-2,6-dione
  参考文献：
  名称：

  桥头羟基双环[2.2.2]辛烷衍生物的合成1

  摘要：

  描述了从1，3-环己二酮开始，向4-羟基双环[2.2.2]辛烷-2，6-二酮衍生物3的两个独立的合成路线。

  DOI：

  10.1021/jo051284e

文献信息

• 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
  作者：Sophie Manner、Cecilia Hansson、Johanna M. Larsson、Viveca T. Oltner、Torbjörn Frejd

  DOI：10.1016/j.tetasy.2010.06.003

  日期：2010.6

  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.