(Z)-dec-5-ene-2,9-dione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-dec-5-ene-2,9-dione
• 英文别名: (Z)-5-decene-2,9-dione
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: DKZLZTWKWHDCAM-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5-已烯-2-酮 在 Grubbs catalyst first generation 作用下， 以 二氯甲烷 为溶剂， 生成 (5E)-5-癸烯-2,9-二酮 、 (Z)-dec-5-ene-2,9-dione
  参考文献：
  名称：

  天然产物合成中的中心对称分子的首次不对称化：制备半短毒素B中的关键片段。

  摘要：

  利用分子对称性可以大大提高合成效率。在半合成毒素B的中心对称AB二氧杂环丁烷片段中嵌入的对称性是在其总合成中首次建立已确定的中间体时进行开发的。通过对映选择性环氧化物水解，然后进行丙酮化，对中心对称二环氧化物1进行不对称化反应，得到了已知的合成中间体2。

  DOI：

  10.1002/1521-3773(20011105)40:21<4082::aid-anie4082>3.0.co;2-t

文献信息

• Assessing Synthetic Strategies: Total Syntheses of (±)-Neodolabellane-Type Diterpenoids
  作者：Cory Valente、Michael G. Organ

  DOI：10.1002/chem.200801161

  日期：2008.9.19

  Two strategies, namely a cross-metathesis/ring-closing metathesis and Pd-catalyzed Stille allylation/Nozaki-Hiyama-Kishi coupling, are examined for the preparation of neodolabellane-type diterpenoids 1 and 2. Whereas the first approach possessed synthetic limitations, the latter was successfully employed to provide compounds 1 and 2 in 8.8% (14 steps) and 8% (15 steps) overall yields, respectively

  研究了两种策略，即交叉复分解/闭环复分解和Pd催化的Stille烯丙基化/ Nozaki-Hiyama-Kishi偶联，以制备新十二烷型双萜1和2。后者被成功用于分别提供8.8％（14步）和8％（15步）总收率的化合物1和2。
• First Desymmetrization of a Centrosymmetric Molecule in Natural Product Synthesis: Preparation of a Key Fragment in the Synthesis of Hemibrevetoxin B
  作者：Joanne M. Holland、Mark Lewis、Adam Nelson

  DOI：10.1002/1521-3773(20011105)40:21<4082::aid-anie4082>3.0.co;2-t

  日期：2001.11.5

  of molecular symmetry can greatly improve the efficiency of syntheses. The symmetry embedded in the centrosymmetric AB dioxepane fragment of hemibrevetoxin B was exploited for the first time in the preparation of an established intermediate in its total synthesis. Desymmetrization of the centrosymmetric diepoxide 1 by enantioselective epoxide hydrolysis followed by acetonization gave the known synthetic

  利用分子对称性可以大大提高合成效率。在半合成毒素B的中心对称AB二氧杂环丁烷片段中嵌入的对称性是在其总合成中首次建立已确定的中间体时进行开发的。通过对映选择性环氧化物水解，然后进行丙酮化，对中心对称二环氧化物1进行不对称化反应，得到了已知的合成中间体2。
• New Syntheses of 1,7-Dimethylnonyl Propanoate, the Western Corn Rootworm Pheromone, in Four Different Ways<i>via</i>Cross Metathesis, Alkylation and Coupling Reactions
  作者：Kenji MORI

  DOI：10.1271/bbb.90805

  日期：2010.3.23

  the four stereoisomers of 1,7-dimethylnonyl propanoate, the female sex pheromone of the western corn rootworm (Diabrotica virgifera virgifera LeConte), was synthesized in four different ways by employing one of the following four reactions as the key step: (i) cross metathesis using the Grubbs I catalyst, (ii) cross metathesis using the Grubbs II catalyst, (iii) alkylation of an alkynide anion, and

  通过以下四个反应之一作为关键步骤，以四种不同方式合成了1,7-二甲基壬基丙酸酯（西方玉米根虫（Diabrotica virgifera virgifera LeConte）的雌性信息素）的四种立体异构体的混合物： i）使用Grubbs I催化剂交叉复分解，（ii）使用Grubbs II催化剂交叉复分解，（iii）炔阴离子的烷基化，和（iv）在四氯铜酸二锂存在下的格利雅偶联。尽管交叉复分解方法可以实现信息素的两个短合成（4或6个步骤），但通过格氏试剂偶联，可以实现最便宜和最有效的合成，从而以2％-甲基- 1-丁醇（8步）。
• <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.