Ethyl 2-(5'-Hexenyl)-2-butenoate | 132156-67-3

• 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 2-(5'-Hexenyl)-2-butenoate
• 英文别名: Ethyl 2-ethylideneoct-7-enoate
• CAS: 132156-67-3
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: CTVBWTRWTVPRCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Ethyl 2-(5'-Hexenyl)-2-butenoate 在 氢氧化钾 、 草酰氯 、 三乙胺 作用下， 以 乙醇 、 环己烷 为溶剂， 反应 97.0h， 生成 1-Vinylbicyclo<4.2.0>octan-8-one
  参考文献：
  名称：

  The generation and rearrangement of 2-(diazoacetyl)cyclobutanones: the formation of 5-spirocyclopropyl-2(5H)-furanones

  摘要：

  We describe here a simple synthesis of 2-(diazoacetyl)cyclobutanones and their facile thermal rearrangement to 5-spirocyclopropyl-DELTA-alpha,beta-butenolides. The yield of the rearrangement product is high, and the reaction is completely stereospecific. alpha-Ketenylcyclobutanones have been identified spectroscopically as intermediates, and their rearrangement was studied kinetically. A strained dipolar cyclic transition is proposed for the rearrangement of the alpha-ketenylcyclobutanones to the corresponding 5-spirocyclopropyl-DELTA-alpha,beta-butenolides.

  DOI：

  10.1021/jo00004a022
• 作为产物：
  描述：

  2-丁烯酸乙酯 、 6-溴-1-己烯 在 lithium diisopropyl amide 作用下， 生成 Ethyl 2-(5'-Hexenyl)-2-butenoate
  参考文献：
  名称：

  The generation and rearrangement of 2-(diazoacetyl)cyclobutanones: the formation of 5-spirocyclopropyl-2(5H)-furanones

  摘要：

  We describe here a simple synthesis of 2-(diazoacetyl)cyclobutanones and their facile thermal rearrangement to 5-spirocyclopropyl-DELTA-alpha,beta-butenolides. The yield of the rearrangement product is high, and the reaction is completely stereospecific. alpha-Ketenylcyclobutanones have been identified spectroscopically as intermediates, and their rearrangement was studied kinetically. A strained dipolar cyclic transition is proposed for the rearrangement of the alpha-ketenylcyclobutanones to the corresponding 5-spirocyclopropyl-DELTA-alpha,beta-butenolides.

  DOI：

  10.1021/jo00004a022

文献信息

• Cp₂TiCl-Promoted <i>Endo-Trig</i> Radical Cyclization to Six- and Seven-Membered Carbocycles: Synthesis of (±)-Isoclavukerin A
  作者：Sabnam Begum、Rajarshi Bhattacharya、Shashwati Paul、Tushar Kanti Chakraborty

  DOI：10.1021/acs.joc.3c01356

  日期：2023.9.1

  investigate the less explored endo-trig radical cyclization in activated olefin-appended epoxides using Cp2TiCl. The radical generated by the Ti(III)-promoted reductive opening of the epoxy ring promptly underwent endo-trig cyclization, giving access to differently 1,3-disubstituted six- and seven-membered carbocycles in good yields and diastereoselectivity. This protocol was successfully employed

  进行了一项系统研究，以研究使用 Cp 2 TiCl在活化的烯烃附加环氧化物中探索较少的内触发自由基环化。Ti(III) 促进的环氧环还原开环产生的自由基迅速进行内三环化，以良好的产率和非对映选择性获得不同的 1,3-二取代六元和七元碳环。该方案已成功用于构建 5,7- 和 6,7- 融合双环框架，需要从头合成属于三正愈创木烷类倍半萜烯天然产物的 (±)-isoclavukerin A，只需八个简单步骤即可市售起始材料。除了 Ti(III) 介导的反应作为合成中的关键步骤外，烯丙基次磺酸盐中间体的连续[2,3]-同向重排/顺式消除成功地在氢化甘菊环核心中形成了高度受限的二烯部分。目标分子。