ethyl 1-[(E)-4-bromobut-2-enyl]-2-oxocycloheptane-1-carboxylate | 204990-67-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 1-[(E)-4-bromobut-2-enyl]-2-oxocycloheptane-1-carboxylate
• CAS: 204990-67-0
• 化学式: C₁₄H₂₁BrO₃
• 分子量: 317.223
• InChiKey: GVTDEEDIWVPCOO-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  ethyl 1-[(E)-4-bromobut-2-enyl]-2-oxocycloheptane-1-carboxylate 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 25.0~600.0 ℃ 、1.33 Pa 条件下， 反应 0.08h， 生成 (1R,6R)-11-Oxo-bicyclo[4.4.1]undec-3-ene-1-carboxylic acid ethyl ester
  参考文献：
  名称：

  Synthesis of Bicyclo[4.n.1]alkanones

  摘要：

  Cyclic P-keto ester monoanions react with 1,4-dihalobutenes to give C-alkylated products which subsequently undergo a stereoselective S(N)2' O-alkylation reaction to yield functionalized enol ethers. When the starting material was ethyl cyclopentanone carboxylate, the C-alkylated product, treated with a base, directly afforded the functionalized bicyclo[4.2.1]nonanone. The enol ethers were submitted to a flash vacuum thermolysis (FVT) reaction to readily afford functionalized bicyclo[4.n.1] alkanones (n = 3, 4). This reaction sequence was applied to the synthesis of a functionalized tricyclo[7.4.1.0(1,5)]tetradecanone, which represents an analogue to the tricyclic core of ingenol.

  DOI：

  10.1021/jo048923q
• 作为产物：
  描述：

  2-氧代环庚烷甲酸乙酯 、 1,4-二溴-2-丁烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以50%的产率得到ethyl 1-[(E)-4-bromobut-2-enyl]-2-oxocycloheptane-1-carboxylate
  参考文献：
  名称：

  金属介导的两原子碳环在水性介质中的扩增

  摘要：

  已经在水性介质中研究了1，3-二羰基化合物的铟和锡介导的羰基烯丙基化。该研究导致开发了一种新颖的在水中的两原子碳环扩大反应。五元，六元，七元，八元和十二元环被两个碳原子分别扩大为七元，八元，九元，十元和十四元环衍生物。Tetralone衍生物也类似地扩展到6-8个稠环系统。和茚满酮衍生物扩展到5-7个稠环系统。铟和锌作为金属介体的使用成功地提供了扩环产品。发现使用水作为溶剂对于扩环反应是必不可少的。

  DOI：

  10.1016/s0040-4020(98)00004-0

文献信息

• Synthesis of Bicyclo[4.<i>n</i>.1]alkanones
  作者：Joaquin Montalt、Frédéric Linker、Frédéric Ratel、Michel Miesch

  DOI：10.1021/jo048923q

  日期：2004.10.1

  Cyclic P-keto ester monoanions react with 1,4-dihalobutenes to give C-alkylated products which subsequently undergo a stereoselective S(N)2' O-alkylation reaction to yield functionalized enol ethers. When the starting material was ethyl cyclopentanone carboxylate, the C-alkylated product, treated with a base, directly afforded the functionalized bicyclo[4.2.1]nonanone. The enol ethers were submitted to a flash vacuum thermolysis (FVT) reaction to readily afford functionalized bicyclo[4.n.1] alkanones (n = 3, 4). This reaction sequence was applied to the synthesis of a functionalized tricyclo[7.4.1.0(1,5)]tetradecanone, which represents an analogue to the tricyclic core of ingenol.
• Metal-mediated two-atom carbocycle enlargement in aqueous medium
  作者：Chao-Jun Li、Dong-Li Chen、Yue-Qi Lu、John X. Haberman、Joel T. Mague

  DOI：10.1016/s0040-4020(98)00004-0

  日期：1998.3

  fourteen-membered ring derivatives respectively. Tetralone derivatives are similarly expanded to 6–8 fused ring systems; and indanone derivatives are expanded to 5–7 fused ring systems. The use of both indium and zinc as the metal mediators provided the ring expansion products successfully. The use of water as a solvent was found to be essential for the ring expansion reaction.

  已经在水性介质中研究了1，3-二羰基化合物的铟和锡介导的羰基烯丙基化。该研究导致开发了一种新颖的在水中的两原子碳环扩大反应。五元，六元，七元，八元和十二元环被两个碳原子分别扩大为七元，八元，九元，十元和十四元环衍生物。Tetralone衍生物也类似地扩展到6-8个稠环系统。和茚满酮衍生物扩展到5-7个稠环系统。铟和锌作为金属介体的使用成功地提供了扩环产品。发现使用水作为溶剂对于扩环反应是必不可少的。