(2Z)-ethyl 3-(pentamethylphenyl)cinnamate

• 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: (2Z)-ethyl 3-(pentamethylphenyl)cinnamate
• 英文别名: ethyl (Z)-3-pentamethylphenyl-3-phenylpropenoate；ethyl (2Z)-3-(pentamethylphenyl)-3-phenylpropenoate；ethyl (Z)-3-(2,3,4,5,6-pentamethylphenyl)-3-phenylprop-2-enoate
• 化学式: C₂₂H₂₆O₂
• 分子量: 322.447
• InChiKey: SWAREFXCRWDBML-MOSHPQCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  五甲基苯 、 苯丙炔酸乙酯 在 silver tetrafluoroborate 、 tetrafluoroboric acid 、 1,3-双(2,6-二-异丙基苯基)咪唑-2-亚基金(I)氯化物 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 5.0h， 以58%的产率得到(2Z)-ethyl 3-(pentamethylphenyl)cinnamate
  参考文献：
  名称：

  炔烃加氢芳基化与 Au N-杂环卡宾催化剂。

  摘要：

  具有 N-杂环卡宾 (NHC) 配体的单核和双核金配合物已被用作炔烃与简单未官能化芳烃的分子间加氢芳基化的催化剂。单核和双核金 (III) 配合物都能够催化反应；然而，最好的结果是使用单核金 (I) 络合物 IPrAuCl 获得的。与更常用的钯 (II) 催化剂相比，这种用一当量四氟硼酸银活化的配合物在室温酸性条件下表现出更高的催化活性和选择性。此外，即使在中性条件下，该复合物也是活跃的，尽管程度较小，但与先前发布的复合 AuCl(PPh(3)) 相比，活性较低，但选择性更高。

  DOI：

  10.3762/bjoc.9.29

文献信息

• 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。
• 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)
• Efficient and selective hydroarylation of propiolic acids and their esters with arenes catalyzed by a PtCl2/AgOTf system
  作者：Juzo Oyamada、Tsugio Kitamura

  DOI：10.1016/j.tetlet.2005.03.179

  日期：2005.5

  PtCl2/AgOTf-catalyzed hydroarylation of ethyl propiolate proceeded effectively to give ethyl (2Z)-cinnamate derivatives in good to high yields, without the formation of diethyl (1E,3Z)-4-arylbuta-1,3-diene-1,3-dicarboxylates that was observed in Pd(OAc)2-catalyzed reaction. Especially, PtCl2/AgOTf-catalyzed hydroarylation of propiolic acids proceeded effectively to give (2Z)-cinnamic acids exclusively.

  PtCl2/AgOTf 催化的丙炔酸乙酯的加氢芳基化有效地进行，以良好至高产率得到 (2Z)-肉桂酸乙酯衍生物，而没有形成 (1E,3Z)-4-arylbuta-1,3-diene-1,3 二乙基酯-在 Pd(OAc)2 催化反应中观察到的二羧酸盐。尤其是，PtCl2/AgOTf 催化的丙炔酸加氢芳基化有效地进行，仅得到 (2Z)-肉桂酸。
• Platinum(II) Complexes with Novel Diisocyanide Ligands: Catalysts in Alkyne Hydroarylation
  作者：Daniele Vicenzi、Paolo Sgarbossa、Andrea Biffis、Cristina Tubaro、Marino Basato、Rino A. Michelin、Arianna Lanza、Fabrizio Nestola、Sara Bogialli、Paolo Pastore、Alfonso Venzo

  DOI：10.1021/om400859q

  日期：2013.12.9

  A series of novel diisocyanide ligands (o-CNC6H4O)2Y (diNC-1: Y = P(O)Ph; diNC-2: Y = o-C(O)C6H4C(O); diNC-3: Y = m-C(O)C6H4C(O); diNC-4: Y = C(O)C2H4C(O); diNC-5: Y = trans-C(O)C2H2C(O)) was successfully synthesized by reaction of lithium 2-isocyanophenate (generated in situ from benzoxazole and n-BuLi) and a diacylic or phosphonic dichloride. The corresponding platinum(II) complexes of general formula

  一系列新型二异氰酸酯配体（o -CNC 6 H 4 O）2 Y（diNC-1：Y = P（O）Ph; diNC-2：Y = o -C（O）C 6 H 4 C（O） ； diNC-3：Y = m -C（O）C 6 H 4 C（O）； diNC-4：Y = C（O）C 2 H 4 C（O）； diNC-5：Y =反式-C （O）C 2 H 2 C（O））是由2-异氰基锂（由苯并恶唑和n -BuLi原位生成）与二酰基或膦酸二氯化物反应成功合成的。相应的通式为[PtX 2的铂（II）配合物（diNC）]通过在起始[PtX 2（COD）]络合物中简单取代1,5-环辛二烯来分离1,2（X = Cl，Me; diNC =二异氰酸酯配体）。通过单晶X射线分析证实了复合物的结构，单核或双核。还可以得到具有（μ-diNC）[顺式-PtCl 2（PPh 3）] 2 }的双核配合物，该二核配合物具有刚性的富芳基
• 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.