diethyl (1E,3Z)-4-(2,4,6-trimethylphenyl)buta-1,3-diene-1,3-dicarboxylate | 289473-83-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: diethyl (1E,3Z)-4-(2,4,6-trimethylphenyl)buta-1,3-diene-1,3-dicarboxylate
• 英文别名: diethyl (2E,4Z)-4-[(2,4,6-trimethylphenyl)methylene]-2-pentenedioate；diethyl (2E,4Z)-4-(2,4,6-trimethylbenzylidene)pent-2-enedioate；(2E,4Z)-ethyl 4-(ethoxycarbonyl)-5-mesityl-2,4-pentadienoate；diethyl (E,4Z)-4-[(2,4,6-trimethylphenyl)methylidene]pent-2-enedioate
• CAS: 289473-83-2
• 化学式: C₁₉H₂₄O₄
• 分子量: 316.397
• InChiKey: KKTZYOJBCKOIHL-YCBPJFTGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  丙炔酸乙酯 、 diethyl (1E,3Z)-4-(2,4,6-trimethylphenyl)buta-1,3-diene-1,3-dicarboxylate 在 [Pd(OAc)₂(dppe)] 、 三氟乙酸 作用下， 反应 5.0h， 以76%的产率得到(2E,4Z,2'E,4'Z)-4,4'-[(2,4,6-trimethylbenzene-1,3-diyl)di(Z)methylidene]bispent-2-enedioate
  参考文献：
  名称：

  Regio- and Stereocontrolled Reaction of Arenes with Ethyl Propiolate Catalyzed by Palladium or Platinum Complexes with a Bidentate Phosphine Ligand. An Efficient and Straightforward Synthesis of (1Z,3E)-1-Aryl-1,3-butadienes

  摘要：

  在30°C下，使用[Pd(dppe)(OAc)2]催化剂，在TFA中，间三甲苯与乙基丙二酸乙酯反应5小时，选择性地生成了二乙基(2E,4Z)-4-[(2,4,6-三甲基苯基)亚甲基]-2-戊二烯二酸酯。筛选多种双齿膦配体表明，dppe和dppm配体有利于芳基丁二烯的形成。此反应应用于其他富电子芳烃，发现对于芳基丁二烯和扩展π共轭分子的合成是有效的。通过NMR和单晶X射线结构分析确认了芳烃对丙二酸酯的区域和立体选择性加成，表明芳基丁二烯的形成包括芳烃和一个金属对乙基丙二酸酯三键的反式加成，随后对另一分子乙基丙二酸酯进行顺式加成。类似地，使用[Pt(dppe)(OTf)2]催化剂，在多种芳烃与乙基丙二酸酯的反应中，选择性地生成了芳基丁二烯。在Pd或Pt催化的芳烃与乙基丙二酸酯反应中，发现双齿配体控制了反应，引导芳基丁二烯的形成。

  DOI：

  10.1246/bcsj.20120233
• 作为产物：
  描述：

  丙炔酸乙酯 、 均三甲苯 在 [Pt(1,2-bis(diphenylphosphino)ethane)(OTf)2] 、 三氟乙酸 作用下， 反应 5.0h， 以79%的产率得到diethyl (1E,3Z)-4-(2,4,6-trimethylphenyl)buta-1,3-diene-1,3-dicarboxylate
  参考文献：
  名称：

  Regio- and Stereocontrolled Reaction of Arenes with Ethyl Propiolate Catalyzed by Palladium or Platinum Complexes with a Bidentate Phosphine Ligand. An Efficient and Straightforward Synthesis of (1Z,3E)-1-Aryl-1,3-butadienes

  摘要：

  在30°C下，使用[Pd(dppe)(OAc)2]催化剂，在TFA中，间三甲苯与乙基丙二酸乙酯反应5小时，选择性地生成了二乙基(2E,4Z)-4-[(2,4,6-三甲基苯基)亚甲基]-2-戊二烯二酸酯。筛选多种双齿膦配体表明，dppe和dppm配体有利于芳基丁二烯的形成。此反应应用于其他富电子芳烃，发现对于芳基丁二烯和扩展π共轭分子的合成是有效的。通过NMR和单晶X射线结构分析确认了芳烃对丙二酸酯的区域和立体选择性加成，表明芳基丁二烯的形成包括芳烃和一个金属对乙基丙二酸酯三键的反式加成，随后对另一分子乙基丙二酸酯进行顺式加成。类似地，使用[Pt(dppe)(OTf)2]催化剂，在多种芳烃与乙基丙二酸酯的反应中，选择性地生成了芳基丁二烯。在Pd或Pt催化的芳烃与乙基丙二酸酯反应中，发现双齿配体控制了反应，引导芳基丁二烯的形成。

  DOI：

  10.1246/bcsj.20120233

文献信息

• 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。
• Drastic effect of bidentate phosphine ligands on Pd-catalyzed hydroarylation of ethyl propiolate: a simple route to arylbutadienes
  作者：Juzo Oyamada、Tsugio Kitamura

  DOI：10.1039/b810658d

  日期：——

  Palladium complexes with bidentate phosphine ligands, Pd(dppe)(OAc)2 and Pd(dppm)(OAc)2, were found to be effective catalysts for reactions of simple arenes with ethyl propiolate, affording arylbutadiene derivatives selectively.

  具有双齿膦配体的钯络合物，即Pd(dppe)(OAc)2和Pd(dppm)(OAc)2，被发现是对简单芳烃与丙炔酸乙酯反应的有效催化剂，能够选择性地生成芳基丁二烯衍生物。
• 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.
• Highly selective hydroarylation of propiolic acid derivatives using a PtCl2/AgOTf catalytic system
  作者：Juzo Oyamada、Tsugio Kitamura

  DOI：10.1016/j.tet.2007.09.076

  日期：2007.12

  Hydroarylation of propiolic acid derivatives with arenes in trifluoroacetic acid efficiently proceeded in the presence Of PtCl2/AgOTf catalyst to give cis-cinnamic acid derivatives in good to high yields. This PtCl2/AgOTf-catalyzed reaction did not afford any 4-arylbuta-1,3-diene-1,3-dicarboxylic acid derivatives formed by Pd(OAc)(2)-catalyzed hydroarylation. The specific optimization of the catalytic hydroarylation and application to electron-rich arenes are reported. (c) 2007 Elsevier Ltd. All rights reserved.