2-benzoyl-6-heptynoic acid methyl ester | 1170144-53-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-benzoyl-6-heptynoic acid methyl ester
• 英文别名: Methyl 2-benzoylhept-6-ynoate；methyl 2-benzoylhept-6-ynoate
• CAS: 1170144-53-2
• 化学式: C₁₅H₁₆O₃
• 分子量: 244.29
• InChiKey: HNCFZVSNJFVUME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-benzoyl-6-heptynoic acid methyl ester 在 重水 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 4.5h， 以82%的产率得到methyl 2-benzoyl(2-²H)hept-6-ynoate
  参考文献：
  名称：

  Cinchona衍生的氨基尿素预催化剂和CuI催化对映选择性Conia-Ene反应的机理研究

  摘要：

  由金鸡纳衍生的氨基脲预催化剂和铜（I）盐的组合可有效催化炔烃系β-酮酸酯的对映选择性Conia-ene环化反应。反应范围广，并且可以高产率和对映选择性地有效地环化一系列底物。本文中，我们基于实验考虑因素和量子力学计算提出了详细的力学研究。已经彻底研究了一些变量，例如有机预催化剂的性质和金属离子源。动力学研究以及动力学同位素效应和氘标记实验已被用于进一步了解机理并证明催化系统的协同性质。我们的研究表明，该反应的限速步骤涉及β-酮酸酯的去质子化，而负责对映体确定步骤的活性物质在氨基脲预催化剂中是单体的。计算研究提供了对观察到的立体感应的定量理解，并确定了来自尿素基团的氢键是确定观察到的对映选择性的关键因素。

  DOI：

  10.1002/chem.201200832
• 作为产物：
  描述：

  5-氯戊炔 、 苯甲酰乙酸甲酯 在 sodium hydride 、 potassium iodide 作用下， 生成 2-benzoyl-6-heptynoic acid methyl ester
  参考文献：
  名称：

  Brønsted Base/Lewis Acid Cooperative Catalysis in the Enantioselective Conia-Ene Reaction

  摘要：

  A mutually compatible and cooperative combination of copper(I) triflate and bifunctional 9-amino-9-deoxyepicinchona-derived urea compounds for the enantioselective Conia-ene cyclization of alkyne-tethered beta-ketoester substrates is reported. The reaction is efficient, broad in scope, and easy to perform and allows access to chiral methylenecyclopentane products with high enantiocontrol. The transformation illustrates the concept of combining inactive precatatysts with inactive transition-metal-ion complexes in situ to reversibly create a catalytically active combination of the two.

  DOI：

  10.1021/ja9004859

文献信息

• ORGANOGOLD COMPLEXES AND METHODS FOR MAKING THE SAME
  申请人：Viseux Eddy Michel Elie

  公开号：US20140039200A1

  公开（公告）日：2014-02-06

  The present invention relates to chiral ligands deriving from α- and β-amino acids, and from metal complexes formed from the same. The ligands are useful with catalytic gold complexes, particularly Au(I) complexes.

  本发明涉及从α-和β-氨基酸衍生的手性配体，以及由此形成的金属配合物。这些配体在催化金配合物中特别有用，特别是Au(I)配合物。
• 3,5-Bis(pentafluorosulfanyl)phenylboronic acid: A new organocatalyst for Conia-ene carbocyclization of 1,3-dicarbonyl compounds having terminal alkynes
  作者：Yu-Dong Yang、Xu Lu、Etsuko Tokunaga、Norio Shibata

  DOI：10.1016/j.jfluchem.2012.06.007

  日期：2012.11

  3,5-Bis(pentafluorosulfanyl)phenylboronic acid 1 was introduced as an efficient organocatalyst for Conia-ene carbocyclization of 1,3-dicarbonyl compounds having terminal alkynes. A variety of 2-alkynic 1,3-dicarbonyl compounds were smoothly converted to ene-carbocyclization products in moderate to excellent yields. Compared with the reported catalyst, 3-nitro phenylboronic acid, catalyst 1 is slightly better in a non-polar solvent such as toluene and Solkane(R) 365mfc (1,1,1,3,3-pentafluorobutane). These results indicate that the SF5 function can be a lipophilic and sterically demanding alternative to the NO2 group in catalyst design. (C) 2012 Elsevier B.V. All rights reserved.
• Brønsted Base/Lewis Acid Cooperative Catalysis in the Enantioselective Conia-Ene Reaction
  作者：Ting Yang、Alessandro Ferrali、Filippo Sladojevich、Leonie Campbell、Darren J. Dixon

  DOI：10.1021/ja9004859

  日期：2009.7.8

  A mutually compatible and cooperative combination of copper(I) triflate and bifunctional 9-amino-9-deoxyepicinchona-derived urea compounds for the enantioselective Conia-ene cyclization of alkyne-tethered beta-ketoester substrates is reported. The reaction is efficient, broad in scope, and easy to perform and allows access to chiral methylenecyclopentane products with high enantiocontrol. The transformation illustrates the concept of combining inactive precatatysts with inactive transition-metal-ion complexes in situ to reversibly create a catalytically active combination of the two.
• Mechanistic Investigations into the Enantioselective Conia-Ene Reaction Catalyzed by Cinchona-Derived Amino Urea Pre-Catalysts and Cu^I
  作者：Filippo Sladojevich、Ángel L. Fuentes de Arriba、Irene Ortín、Ting Yang、Alessandro Ferrali、Robert S. Paton、Darren J. Dixon

  DOI：10.1002/chem.201200832

  日期：2013.10.11

  Conia‐ene cyclization of alkyne‐tethered β‐ketoesters is efficiently catalyzed by the combination of cinchona‐derived amino‐urea pre‐catalysts and copper(I) salts. The reaction scope is broad and a series of substrates can be efficiently cyclized with high yields and enantioselectivities. Herein, we present a detailed mechanistic study based on experimental considerations and quantum mechanical calculations

  由金鸡纳衍生的氨基脲预催化剂和铜（I）盐的组合可有效催化炔烃系β-酮酸酯的对映选择性Conia-ene环化反应。反应范围广，并且可以高产率和对映选择性地有效地环化一系列底物。本文中，我们基于实验考虑因素和量子力学计算提出了详细的力学研究。已经彻底研究了一些变量，例如有机预催化剂的性质和金属离子源。动力学研究以及动力学同位素效应和氘标记实验已被用于进一步了解机理并证明催化系统的协同性质。我们的研究表明，该反应的限速步骤涉及β-酮酸酯的去质子化，而负责对映体确定步骤的活性物质在氨基脲预催化剂中是单体的。计算研究提供了对观察到的立体感应的定量理解，并确定了来自尿素基团的氢键是确定观察到的对映选择性的关键因素。