endo-2-Pivaloylbicyclo<3.3.0>oct-6-ene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: endo-2-Pivaloylbicyclo<3.3.0>oct-6-ene
• 英文别名: 1-[(1S,3aS,6aR)-1,2,3,3a,6,6a-hexahydropentalen-1-yl]-2,2-dimethylpropan-1-one
• 化学式: C₁₃H₂₀O
• 分子量: 192.301
• InChiKey: JFFKHOPYBLKFKL-MXWKQRLJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1,5-cis,cis-cyclooctadiene 、 pivaloyl fluoride 在 三氟化硼 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 endo-2-Pivaloylbicyclo<3.3.0>oct-6-ene 、 endo-2-Pivaloylbicyclo<3.3.0>oct-7-ene 、 endo-2-Pivaloyl-endo-7-hydroxybicyclo<3.3.0>octane 、 endo-2-Pivaloyl-endo-8-hydroxybicyclo<3.3.0>octane
  参考文献：
  名称：

  Acylation of 1,5-Cyclooctadiene with Pivaloyl Tetrafluoroborate. Stereoselective Synthesis of endo-2-Pivaloyl-endo-8- hydroxybicyclo[3.3.0]octane. Study of the Reaction Mechanism

  摘要：

  Reaction of (Z,Z)-1,5-cyclooctadiene (1) with pivaloyl tetrafluoroborate at -78 degrees C gives endo-2-pivaloylbicyclo[3.3.0]oct-7-ene (2) and endo-2-pivaloylbicyclo[3.3.0]oct-7-ene (3) in a 5:1 ratio. If the reaction mixture was stored at room temperature before hydrolysis, a mixture of hydroxy ketones 4-6 is obtained. The ratio for compounds 4-6 depends on the particular temperature conditions; to give pure endo-2-pivaloyl-endo-8-hydroxybicyclo[3.3.0]octane 4, the reaction mixture was refluxed at 42 degrees C for 36 h before hydrolysis. The NMR study of the reaction mixture showed that the primary product is protonated ketone 8 equilibrating with its isomer 7 via protonation-deprotonation. At temperatures higher than -20 degrees C, 7 and 8 give rise to a mixture of carboxonium salts 9-11, which rearrange into pure 9 after prolonged reflux.

  DOI：

  10.1021/jo00129a022

文献信息

• Acylation of 1,5-Cyclooctadiene with Pivaloyl Tetrafluoroborate. Stereoselective Synthesis of endo-2-Pivaloyl-endo-8- hydroxybicyclo[3.3.0]octane. Study of the Reaction Mechanism
  作者：Ilya D. Gridnev

  DOI：10.1021/jo00129a022

  日期：1995.12

  Reaction of (Z,Z)-1,5-cyclooctadiene (1) with pivaloyl tetrafluoroborate at -78 degrees C gives endo-2-pivaloylbicyclo[3.3.0]oct-7-ene (2) and endo-2-pivaloylbicyclo[3.3.0]oct-7-ene (3) in a 5:1 ratio. If the reaction mixture was stored at room temperature before hydrolysis, a mixture of hydroxy ketones 4-6 is obtained. The ratio for compounds 4-6 depends on the particular temperature conditions; to give pure endo-2-pivaloyl-endo-8-hydroxybicyclo[3.3.0]octane 4, the reaction mixture was refluxed at 42 degrees C for 36 h before hydrolysis. The NMR study of the reaction mixture showed that the primary product is protonated ketone 8 equilibrating with its isomer 7 via protonation-deprotonation. At temperatures higher than -20 degrees C, 7 and 8 give rise to a mixture of carboxonium salts 9-11, which rearrange into pure 9 after prolonged reflux.