[(E)-16-acetyloxyhexadec-8-enyl] acetate | 1160105-93-0

• 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: [(E)-16-acetyloxyhexadec-8-enyl] acetate
• CAS: 1160105-93-0
• 化学式: C₂₀H₃₆O₄
• 分子量: 340.503
• InChiKey: HLEJLPLVMBUPPB-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  24
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  在 [Ru(pivalate)(CHC6H4OiPr)(C10H14C3H4N2Mes)] 作用下， 以 四氢呋喃 为溶剂， 35.0 ℃ 、506.66 kPa 条件下， 反应 11.5h， 生成 Z-hexa-8-decen-dinyl 1,16-diacetate 、 [(E)-16-acetyloxyhexadec-8-enyl] acetate
  参考文献：
  名称：

  Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory

  摘要：

  The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.

  DOI：

  10.1021/ja4010267

文献信息

• Pheromone synthesis. Part 240: Cross-metathesis with Grubbs I (but not Grubbs II) catalyst for the synthesis of (R)-trogodermal (14-methyl-8-hexadecenal) to study the optical rotatory powers of compounds with a terminal sec-butyl group
  作者：Kenji Mori

  DOI：10.1016/j.tet.2009.02.064

  日期：2009.5

  (R)-Trogodermal (14-methyl-8-hexadecenal), the sex pheromone of Trogoderma species of pest insects against stored products, and its (S)-isomer were synthesized by using olefin cross-metathesis between (R)- or (S)-7-methyl-1-nonene and 8-nonenyl acetate as the key step. This step was successful with Grubbs I but not with Grubbs II catalyst. The latter caused randomization of the carbon skeleton to give

  （- [R）-Trogodermal（14甲基-8-十六碳烯醛），性信息素斑皮蠹属对照存储产品害虫的种类，以及其（小号）通过使用烯烃之间（交叉复分解，合成异构体[R ）-或（S）-7-甲基-1-壬烯和乙酸8-壬烯酯是关键步骤。该步骤对于Grubbs I是成功的，但是对于Grubbs II催化剂却不是成功的。后者导致碳骨架的随机化，从而产生异常产物的混合物，该异常产物具有比所需产物更长或更短的碳链。测量了18种新的和6种先前合成的具有仲仲丁基端基的化合物的比旋光度，得出的结论是[α] D +3.5至+6.5或-3.6至-6.4
• <i>Z</i>-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory
  作者：Hiroshi Miyazaki、Myles B. Herbert、Peng Liu、Xiaofei Dong、Xiufang Xu、Benjamin K. Keitz、Thay Ung、Garik Mkrtumyan、K. N. Houk、Robert H. Grubbs

  DOI：10.1021/ja4010267

  日期：2013.4.17

  The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.