diethyl 1-(p-methoxyphenyl)-6-hepten-1-yne-4,4-dicarboxylate | 234114-58-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: diethyl 1-(p-methoxyphenyl)-6-hepten-1-yne-4,4-dicarboxylate
• 英文别名: Diethyl 2-[3-(4-methoxyphenyl)prop-2-ynyl]-2-prop-2-enylpropanedioate
• CAS: 234114-58-0
• 化学式: C₂₀H₂₄O₅
• 分子量: 344.408
• InChiKey: NGJTWQTYKLOYNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  25
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 1-(p-methoxyphenyl)-6-hepten-1-yne-4,4-dicarboxylate 在 一氧化碳 、 platinum(II) chloride 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、101.32 kPa 条件下， 以58%的产率得到diethyl 6-(4-methoxyphenyl)bicyclo[3.2.0]hept-6-ene-3,3-dicarboxylate
  参考文献：
  名称：

  通过铂催化的烯炔环异构化反应制备环丁烯

  摘要：

  在甲苯中催化量的 PtCl2 存在下，在其炔部分上带有（富电子）芳基取代基的 1,6-烯炔重排为环丁烯衍生物。当在 CO (1 atm) 气氛下进行时，反应显着加速，最有可能是通过临时配位到这种 pi 酸性配体来增加金属模板的亲电性。这种转变允许在产物中建立相当大的应变，如三环骨架的生产性形成所证明的那样，例如 7 或 9。此外，这些产品为先前提出的铂催化的环异构化反应的机制场景提供了证据，这被认为通过模拟金属络合的“非经典”碳正离子反应性的有机铂物种进行。

  DOI：

  10.1021/ja050845g
• 作为产物：
  描述：

  2-烯丙基-2-(2-丙炔基)丙二酸二乙酯 、 4-碘苯甲醚 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以97%的产率得到diethyl 1-(p-methoxyphenyl)-6-hepten-1-yne-4,4-dicarboxylate
  参考文献：
  名称：

  通过铂催化的烯炔环异构化反应制备环丁烯

  摘要：

  在甲苯中催化量的 PtCl2 存在下，在其炔部分上带有（富电子）芳基取代基的 1,6-烯炔重排为环丁烯衍生物。当在 CO (1 atm) 气氛下进行时，反应显着加速，最有可能是通过临时配位到这种 pi 酸性配体来增加金属模板的亲电性。这种转变允许在产物中建立相当大的应变，如三环骨架的生产性形成所证明的那样，例如 7 或 9。此外，这些产品为先前提出的铂催化的环异构化反应的机制场景提供了证据，这被认为通过模拟金属络合的“非经典”碳正离子反应性的有机铂物种进行。

  DOI：

  10.1021/ja050845g

文献信息

• Scope of the Intramolecular Titanocene-Catalyzed Pauson−Khand Type Reaction¹
  作者：Frederick A. Hicks、Natasha M. Kablaoui、Stephen L. Buchwald

  DOI：10.1021/ja990682u

  日期：1999.6.1

  A Pauson−Khand type conversion of enynes to bicyclic cyclopentenones employing the commercially available precatalyst titanocene dicarbonyl is described. This methodology shows excellent functional group tolerance for a group 4 metallocene-catalyzed process. The scope and limitations of this cyclization with respect to 1,6-, 1,7- and 1,8-enynes with a variety of terminal alkyne substituents, chiral

  描述了使用市售的前催化剂二茂钛二羰基将烯炔转化为双环环戊烯酮的 Pauson-Khand 型转化。该方法对第 4 族茂金属催化过程显示出优异的官能团耐受性。详细描述了关于具有各种末端炔烃取代基的 1,6-、1,7- 和 1,8- 烯炔、手性烯炔和含有取代烯烃的烯炔的这种环化的范围和限制。已经提出了涉及中间体钛环戊烯羰基化的机制。
• An Intramolecular Titanium-Catalyzed Asymmetric Pauson−Khand Type Reaction¹
  作者：Frederick A. Hicks、Stephen L. Buchwald

  DOI：10.1021/ja990683m

  日期：1999.8.1

  The development of the first catalytic asymmetric Pauson−Khand type cyclization of enynes is described. The active catalyst, (S,S)-(EBTHI)Ti(CO)2 (1), is generated in situ from (S,S)-(EBTHI)TiMe2 (2). A variety of 1,6-enynes can be converted to the corresponding cyclopentenones in high yield (70−94%) with excellent ee's (87−96%). Limitations of the catalyst with respect to substrate structure are discussed

  描述了烯炔的第一个催化不对称 Pauson-Khand 型环化的发展。活性催化剂 (S,S)-(EBTHI)Ti(CO)2 (1) 是由 (S,S)-(EBTHI)TiMe2 (2) 原位生成的。各种 1,6-烯炔可以以高产率 (70-94%) 转化为相应的环戊烯酮，具有出色的 ee (87-96%)。讨论了催化剂在基材结构方面的局限性。几种烯酮产品的绝对构型已经确定，这些分配代表了与初始报告中分配的逆转。提出了该催化剂的对映选择性的意义和水平的基本原理。
• The Electronic Effect of Ligands on Stereoselectivity in the Rhodium(I)-Catalyzed Asymmetric Pauson-Khand-Type Reaction under a Carbon Monoxide Atmosphere
  作者：Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt、Nakcheol Jeong、Dong Kim、Choong Choi、In Kim、Séverine Jeulin

  DOI：10.1055/s-2006-950369

  日期：2006.12

  of various ligands on the stereoselectivity and reaction rate of the rhodium(I)-catalyzed asymmetric Pauson-Khand-type reaction were examined. We demonstrated that both the reaction rate and the enantioselectivity are significantly dependent on the electron density of the ligands; when ligands bearing deshielded phosphine were utilized, the reaction rate was slower, but the products were obtained with

  基于所提出的机理，研究了各种配体对铑(I)催化的不对称Pauson-Khand型反应的立体选择性和反应速率的电子效应。我们证明了反应速率和对映选择性都显着依赖于配体的电子密度。当使用带有去屏蔽膦的配体时，反应速度较慢，但​​得到的产物对映选择性有所提高。
• 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.
• Asymmetric Pauson−Khand-type Reaction Mediated by Rh(I) Catalyst at Ambient Temperature
  作者：Dong Eun Kim、In Su Kim、Virginie Ratovelomanana-Vidal、Jean-Pierre Genêt、Nakcheol Jeong

  DOI：10.1021/jo801236c

  日期：2008.10.17

  An efficient asymmetric PKR mediated by Rh(I) catalyst at ambient temperature was developed. The reaction utilizing a Rh(I) catalyst bearing a (R)-3,5-diMeC(4)H(4)-BINAP ligand at 18-20 degrees C under a reduced partial pressure of CO (0.1 atm) provided PKR products in high chemical yield as well as high enantioselectivity.