3-(3-Butenyl)-2,4,4-trimethyl-2,5-cyclohexadienone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(3-Butenyl)-2,4,4-trimethyl-2,5-cyclohexadienone
• 英文别名: 3-But-3-enyl-2,4,4-trimethylcyclohexa-2,5-dien-1-one
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: CVYSHBJZMZDCHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2-溴乙基)-1,3-二氧杂环己烷 、 3-(3-Butenyl)-2,4,4-trimethyl-2,5-cyclohexadienone 在 copper(I) bromide dimethylsulfide complex magnesium 作用下， 生成 3-(3-Butenyl)-5-<2-(1,3-dioxan-2-yl)ethyl>-2,4,4-trimethyl-2-cyclohexenone
  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：

  5-(3-Butenyl)-4,4,6-trimethyl-2-cyclohexenone 在 对甲苯磺酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 1,4-二氧六环 为溶剂， 反应 48.0h， 以91%的产率得到3-(3-Butenyl)-2,4,4-trimethyl-2,5-cyclohexadienone
  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

文献信息

• Macrolactonization-transannular aldol condensation approach to the taxane AB ring system
  作者：Ki Byung Chai、Paul Sampson

  DOI：10.1021/jo00076a049

  日期：1993.11

  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.