ethyl (2Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)-2-propenoate

• 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: ethyl (2Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)-2-propenoate
• 英文别名: ethyl (2Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)prop-2-enoate；ethyl (2Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)propenoate；ethyl (Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)propenoate；(2Z)-ethyl (2,4,6-trimethyl-3-hydroxyphenyl)propenoate；ethyl (Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)prop-2-enoate
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: LJTMEZBUQDIRPF-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,4,6-三甲酚 、 丙炔酸乙酯 在 三苯基膦氯金 、 三氟化硼乙醚 作用下， 以 硝基甲烷 为溶剂， 反应 14.0h， 以83%的产率得到ethyl (2Z)-3-(3-hydroxy-2,4,6-trimethylphenyl)-2-propenoate
  参考文献：
  名称：

  炔烃的金催化加氢芳基化

  摘要：

  被取代的富电子芳烃对芳基取代的炔烃的加氢芳基化是由被 AgSbF6 等银盐活化的 AuCl3 催化的。在末端炔烃的情况下，观察到有利于 1,1-二取代烯烃的完全区域选择性。在缺乏电子的炔烃（如乙炔羧酸酯）的情况下，Ag 盐或 BF3·OEt2 活化的金（I）配合物如 [Ph3PAuCl] 是最好的催化剂，导致相反的区域选择性和高度的（Z）选择性. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300260

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。
• A high hydroarylation activity of K2PtCl4/AgOTf catalyst in the reaction of propiolic acid with unactivated and activated arenes
  作者：Juzo Oyamada、Takuya Hashimoto、Tsugio Kitamura

  DOI：10.1016/j.jorganchem.2009.07.008

  日期：2009.10

  hydroarylation with less reactive benzene to give cis-cinnamic acid in good yield. The hydroarylation with toluene gave a higher yield of hydroarylation products than that with benzene and resulted in ortho/para orientation with an almost statistical ratio, suggesting that the result is very close to that of the Friedel-Crafts alkylation with methyl bromide or p-nitrobenzyl chloride. Hydroarylation of propiolic

  在钯和铂催化剂中，混合催化剂K 2 PtCl 4 / AgOTf显示出最高的丙酸加氢芳基化活性。该催化剂可有效地用较少的反应性苯进行加氢芳基化反应，以高收率得到顺式肉桂酸。用甲苯进行氢芳基化反应比使用苯进行氢芳基化反应的收率更高，并导致邻位/对位取向，并且几乎具有统计比例，这表明该结果非常接近于用甲基溴或对硝基苄基进行的Friedel-Crafts烷基化反应的结果。氯化物。在K 2存在下，丙酸与其他富电子芳烃的氢芳基化反应有效进行在三氟乙酸中的PtCl 4 / AgOTf催化剂以良好或高收率形成顺式肉桂酸。该方法也适用于丙酸乙酯的氢芳基化。
• 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。
• 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 (1<i>Z</i>,3<i>E</i>)-1-Aryl-1,3-butadienes
  作者：Juzo Oyamada、Mariko Sakai、Yasunori Yamada、Tsugio Kitamura

  DOI：10.1246/bcsj.20120233

  日期：2013.1.15

  The reaction of mesitylene with ethyl propiolate in the presence of [Pd(dppe)(OAc)2] in TFA at 30 °C for 5 h gave diethyl (2E,4Z)-4-[(2,4,6-trimethylphenyl)methylene]-2-pentenedioate selectively. Screening several bidentate phosphines ligands showed that dppe and dppm ligands are good for the arylbutadiene formation. This reaction was applied to other electron-rich arenes and found to be effective for synthesis of arylbutadienes and extended π-conjugated molecules. The regio- and stereoselective addition of an arene to propiolate was confirmed by NMR and single-crystal X-ray structural analyses of the products, suggesting that the arylbutadiene formation consisted of anti addition of an arene and a metal to the triple bond of ethyl propiolate, followed by syn addition to another molecule of ethyl propiolate. Similarly, the reaction of various arenes with ethyl propiolate in the presence of [Pt(dppe)(OTf)2] catalyst gave arylbutadienes selectively. In the Pd- or Pt-catalyzed reaction of arenes with ethyl propiolate, it was found that a bidentate ligand controlled the reaction to lead the formation of arylbutadienes.

  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。
• 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.