(Z)-1-pentamethylphenyl-1-phenyl-1-propene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-1-pentamethylphenyl-1-phenyl-1-propene
• 英文别名: 1,2,3,4,5-pentamethyl-6-[(Z)-1-phenylprop-1-enyl]benzene
• 化学式: C₂₀H₂₄
• 分子量: 264.411
• InChiKey: YAJALYSVUIANSR-GXHLCREISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-苯基-1-丙炔 、 五甲基苯 在 scandium tris(trifluoromethanesulfonate) 1-n-butyl-3-methylimidazolium hexafluoroantimonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.25h， 以81%的产率得到(Z)-1-pentamethylphenyl-1-phenyl-1-propene
  参考文献：
  名称：

  金属三氟甲磺酸催化离子液体中芳烃与炔烃的区域选择性和立体选择性Friedel-Crafts芳烃的烯化反应：范围和机理

  摘要：

  在金属三氟甲磺酸酯催化的炔烃加氢芳基化中，采用离子液体显着增强了催化活性，从而扩大了底物（芳烃和炔烃）的范围。在某些情况下，甚至在常规有机溶剂中不可能发生的反应在离子液体中也能顺利进行。而且，通过在反应后简单地倾析有机层，可以容易地回收含离子液体的催化剂，并且可以将其重新用于随后的运行中而没有任何明显的活性损失。包括反应中间体的13 C NMR分析和同位素实验在内的机理研究首次证实，这种类型的反应是通过乙烯基阳离子中间体进行的。

  DOI：

  10.1002/adsc.200700039

文献信息

• Thermodynamically- and kinetically-controlled Friedel–Crafts alkenylation of arenes with alkynes using an acidic fluoroantimonate(v) ionic liquid as catalyst
  作者：Doo Seong Choi、Jin Hong Kim、Ueon Sang Shin、Ravindra R. Deshmukh、Choong Eui Song

  DOI：10.1039/b705719a

  日期：——

  By employing superacidic fluoroantimonate ionic liquid (IL), [bmim][Sb2F11], as catalyst, not only thermodynamically-controlled but also kinetically-controlled Friedel–Crafts alkenylations of arenes with alkynes have been realized for the first time.

  通过采用超酸性氟锑酸离子液体（IL）[bmim][Sb2F11]作为催化剂，首次实现了既受热力学控制又受动力学控制的芳香族化合物与炔烃的Friedel-Crafts烯基化反应。
• Metal Triflate-Catalyzed Regio- and Stereoselective Friedel–Crafts Alkenylation of Arenes with Alkynes in an Ionic Liquid: Scope and Mechanism
  作者：Mi Young Yoon、Jin Hong Kim、Doo Seoung Choi、Ueon Sang Shin、Jin Yong Lee、Choong Eui Song

  DOI：10.1002/adsc.200700039

  日期：2007.7.2

  In the metal triflate-catalyzed hydroarylation of alkynes, employing an ionic liquid dramatically enhanced the catalytic activities, resulting in broadening the scope of substrates (arenes and alkynes). In some cases, even reactions that were not possible in conventional organic solvents proceeded smoothly in ionic liquids. Moreover, the ionic liquid phase containing catalyst could be readily recovered

  在金属三氟甲磺酸酯催化的炔烃加氢芳基化中，采用离子液体显着增强了催化活性，从而扩大了底物（芳烃和炔烃）的范围。在某些情况下，甚至在常规有机溶剂中不可能发生的反应在离子液体中也能顺利进行。而且，通过在反应后简单地倾析有机层，可以容易地回收含离子液体的催化剂，并且可以将其重新用于随后的运行中而没有任何明显的活性损失。包括反应中间体的13 C NMR分析和同位素实验在内的机理研究首次证实，这种类型的反应是通过乙烯基阳离子中间体进行的。
• Highly Efficient Alkyne Hydroarylation with Chelating Dicarbene Palladium(II) and Platinum(II) Complexes
  作者：Andrea Biffis、Cristina Tubaro、Gabriella Buscemi、Marino Basato

  DOI：10.1002/adsc.200700271

  日期：2008.1.4

  reaction protocol for the coupling of arenes with alkynes (the Fujiwara reaction), yielding products of formal trans-hydroarylation of the triple bond. The protocol makes use of a chelating N-heterocyclic dicarbene palladium(II) complex as catalyst and allows us to perform the reaction in a few hours with only 0.1 mol % catalyst yielding the trans-hydroarylation product in high yields and with excellent selectivity

  1我们报道了一种用于芳烃与炔烃偶联的新型反应方案（藤原反应），产生了三键形式的正式反式-氢芳基化反应的产物。该方案利用螯合的N-杂环二碳烯钯（II）配合物作为催化剂，使我们能够在数小时内用仅0.1 mol％的催化剂进行反应，从而生成反式-氢芳基化产物的收率高且具有优异的选择性。我们讨论了该反应方案的适用性，尽管仅限于富含电子的芳烃，但目前对于炔烃而言，该方案相当普遍。我们还提出了关于卡宾单元中氮取代基，卡宾单元之间的桥联基团和配位阴离子配体的催化剂优化结果。最后，我们还讨论了相关的铂（II）螯合二卡宾络合物的催化性能。
• Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening
  作者：Andrea Biffis、Luca Gazzola、Pierangelo Gobbo、Gabriella Buscemi、Cristina Tubaro、Marino Basato

  DOI：10.1002/ejoc.200900321

  日期：2009.7

  Palladium(II) complexes with a ligand set made from a chelating N-heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room-temperature hydroarylation of alkynes at low catalyst loading (0.1 mol-%). Moreover, the screening of various strong acids

  发现钯 (II) 与由螯合 N-杂环双卡宾配体和两个弱配位阴离子（通常在添加 2 当量合适的银盐后原位引入）制成的配体组的配合物是非常活跃和选择性的催化剂在低催化剂负载量 (0.1 mol-%) 下炔烃的室温加氢芳基化。此外，各种强酸作为反应促进剂的筛选表明，酸的强度和其共轭碱的配位能力都会影响催化性能。最显着的是，HBF4 与二卡宾 Pd 络合物催化剂一起使用使反应的选择性发生了巨大变化，由于两分子炔烃插入芳族 C-H 键，产物的普遍形成。本文中呈现的结果强调了这样一个事实，即双卡宾配体除了稳定催化剂外，还能够提高催化活性，最值得注意的是，将反应选择性导向新产品。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Novel Pd(II)- and Pt(II)-Catalyzed Regio- and Stereoselective <i>trans</i>-Hydroarylation of Alkynes by Simple Arenes
  作者：Chengguo Jia、Wenjun Lu、Juzo Oyamada、Tsugio Kitamura、Kenji Matsuda、Masahiro Irie、Yuzo Fujiwara

  DOI：10.1021/ja0005845

  日期：2000.8.1

  Efficient trans-hydroarylation of alkynes by simple arenes has been realized regio- and stereoselectively at room temperature in the presence of Pd(II) or Pt(II) catalysts and a mixed solvent containing trifluoroacetic acid (TFA). Various arenes undergo trans-hydroarylation selectively across terminal and internal C-C triple bonds-including those conjugated to CHO, COMe, CO2H, and CO2Et groups, affording kinetically controlled cis-arylalkenes predominantly in most cases, especially, in good yields for electron-rich arenes and activated alkynes. The formation of arene/alkyne 1/2 or 2/1 adducts as side products is dependent on the arenes' and alkynes' substituents, which can be suppressed in some cases by changing the catalyst, catalyst concentration, and reaction time. The Pt(II) system, PtCl2/2AgOAc/TFA, shows lower catalytic activity than Pd(OAc)(2)/TFA, but higher selectivity, giving higher yields of adducts at the same conversion. On the basis of several isotope experiments and control reactions, a possible mechanism involving electrophilic metalation of aromatic C-H bonds by in-situ-generated cationic Pd(II) and Pt(II) species leading to intermolecular trans-arylpalladation to alkynes has been discussed.