(2-octynyl)-(2-propenyl)propanedioic acid diethyl ester | 350248-68-9

• 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: (2-octynyl)-(2-propenyl)propanedioic acid diethyl ester
• 英文别名: diethyl 2-allyl-2-(oct-2-ynyl)malonate；Diethyl 2-oct-2-ynyl-2-prop-2-enylpropanedioate
• CAS: 350248-68-9
• 化学式: C₁₈H₂₈O₄
• 分子量: 308.418
• InChiKey: TVKDNXLHHPDKMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2-octynyl)-(2-propenyl)propanedioic acid diethyl ester 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以75%的产率得到(E)-3-hexylidene-4-methylene-cyclopentane-1,1-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  铱催化的烯炔的环异构化。

  摘要：

  DOI：

  10.1021/jo010091y
• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 、 1-溴-2辛炔 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以81%的产率得到(2-octynyl)-(2-propenyl)propanedioic acid diethyl ester
  参考文献：
  名称：

  铱催化的烯炔的环异构化。

  摘要：

  DOI：

  10.1021/jo010091y

文献信息

• Skeletal Reorganization of Enynes Catalyzed by InCl₃
  作者：Yuhei Miyanohana、Naoto Chatani

  DOI：10.1021/ol060606d

  日期：2006.5.1

  [reaction: see text] The skeletal reorganization of enynes is achieved by the presence of InCl(3) as the catalyst. The reaction of enynes having a terminal acetylenic moiety proceeds in a stereospecific manner to give 1-vinylcycloalkenes. The reaction of enynes containing an alkyl group on the acetylenic terminal carbon resulted in a new type of skeletal reorganization to give 1-allylcycloalkenes,

  [反应：见正文]通过存在InCl（3）作为催化剂可实现烯炔的骨架重组。具有末端炔部分的烯炔的反应以立体有择方式进行，得到1-乙烯基环烯烃。在炔属末端碳上包含烷基的烯炔的反应导致了新型的骨架重组，从而生成了1-烯丙基环烯烃，该烯丙基环烯烃的形成涉及CC双键和三键的双裂解。
• 2,2′‐Bis[bis(3,5‐di‐<i>tert</i>‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl in Intramolecular Rhodium(I)‐Catalyzed Asymmetric Pauson–Khand‐Type Reactions
  作者：Dong Eun Kim、Virginie Ratovelomanana‐Vidal、Nakcheol Jeong

  DOI：10.1002/adsc.201000221

  日期：2010.10.9

  AbstractA cationic rhodium(I)/2,2′‐bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl (DTBM‐MeO‐BIPHEP) catalyst was highly efficient for the asymmetric catalytic Pauson–Khand reaction, especially for those substrates containing aryl group‐substituted alkynes. The formation of the products that were derived from a β‐hydride eliminated intermediate 5 was completely suppressed over a wide range of substrates. This reaction was a serious process competing reaction with the migratory CO insertion that led to the Pauson–Khand reaction product and often substantially ruined the chemical yield of the Pauson–Khand reaction. The advantages of this system were clearly demonstrated for previously troublesome substrates, N‐tosyl‐ (1b) and malonate‐tethered 1,6‐enynes (1c), that exhibited a higher enantioselectivity without a loss in the chemical yields. The obvious beneficial effects were attributed to the synergic effect of various factors, such as the electron density of the phosphorus of the ligand, the dihedral angles of the atropisomeric ligand, and the substitution on the phosphine aryl rings which play a crucial role in the stereochemical outcome of Rh‐catalyzed Pauson–Khand reaction.
• Iridium(I)-Catalyzed Cycloisomerization of Enynes
  作者：Naoto Chatani、Hiroki Inoue、Tsumoru Morimoto、Toyoshige Muto、Shinji Murai

  DOI：10.1021/jo010091y

  日期：2001.6.1