12,14,14-Trimethyl-5-oxobicyclo<8.3.1>tetradeca-12-ene-3,6,11-trione | 151775-31-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 12,14,14-Trimethyl-5-oxobicyclo<8.3.1>tetradeca-12-ene-3,6,11-trione
• 英文别名: 11,14,14-trimethyl-5-oxabicyclo[8.3.1]tetradec-10-ene-4,7,12-trione
• CAS: 151775-31-4
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: PIUOPUORDJAENR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  60.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  12,14,14-Trimethyl-5-oxobicyclo<8.3.1>tetradeca-12-ene-3,6,11-trione 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 2.0h， 以51%的产率得到5-Oxa-11,14,14-trimethyltetracyclo<8.3.1.0^3,7>tetradeca-3(7),10-diene-4,12-dione
  参考文献：
  名称：

  Macrolactonization-transannular aldol condensation approach to the taxane AB ring system

  摘要：

  Cyclohexenone 13, containing the fully elaborated taxane A ring, was prepared from 4,4-dimethyl-2-cyclohexenone (43% for four steps); two copper-catalyzed Grignard conjugate addition reactions on crowded dienones 8 and 11 were employed as key transformations. Elaboration of 13 to the chloro keto acid 6 was achieved via an epoxidation/regioselective chloride-mediated epoxide ring opening/Jones oxidation protocol (42% for three steps). Macrolactonization (59%) followed by chemoselective transannular aldol condensation within the resulting 11-membered bicyclic keto lactone 4 under thermodynamic control (51%) resulted in closure of the taxane B ring to afford the target 2(5H)-furanone 3.

  DOI：

  10.1021/jo00076a049
• 作为产物：
  描述：

  3-(3-Butenyl)-5-<2-(1,3-dioxan-2-yl)ethyl>-2,4,4-trimethyl-2-cyclohexenone 在 chromium(VI) oxide 、 sodium hydroxide 、 硫酸 、 溶剂黄146 、 间氯过氧苯甲酸 、 lithium chloride 作用下， 以 四氢呋喃 、 二甲基亚砜 、 丙酮 为溶剂， 反应 70.0h， 生成 12,14,14-Trimethyl-5-oxobicyclo<8.3.1>tetradeca-12-ene-3,6,11-trione
  参考文献：
  名称：

  Macrolactonization-transannular aldol condensation approach to the taxane AB ring system

  摘要：

  Cyclohexenone 13, containing the fully elaborated taxane A ring, was prepared from 4,4-dimethyl-2-cyclohexenone (43% for four steps); two copper-catalyzed Grignard conjugate addition reactions on crowded dienones 8 and 11 were employed as key transformations. Elaboration of 13 to the chloro keto acid 6 was achieved via an epoxidation/regioselective chloride-mediated epoxide ring opening/Jones oxidation protocol (42% for three steps). Macrolactonization (59%) followed by chemoselective transannular aldol condensation within the resulting 11-membered bicyclic keto lactone 4 under thermodynamic control (51%) resulted in closure of the taxane B ring to afford the target 2(5H)-furanone 3.

  DOI：

  10.1021/jo00076a049