(E)-ethyl 2-oxo-4-p-tolylbut-3-enoate | 768383-25-1

• 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: (E)-ethyl 2-oxo-4-p-tolylbut-3-enoate
• 英文别名: ethyl (E)-2-oxo-4-(p-tolyl)but-3-enoate；ethyl (E)-4-(4-methylphenyl)-2-oxobut-3-enoate
• CAS: 768383-25-1
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: DRORBGSVPJZIQY-CMDGGOBGSA-N

物化性质

• 熔点：
  47-48 °C
• 沸点：
  336.6±35.0 °C(Predicted)
• 密度：
  1.108±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  (E)-ethyl 2-oxo-4-p-tolylbut-3-enoate 在 盐酸 、 [NH2Me2]+[{RuCl[(S)-SunPhos]}2(μ-Cl3)] 、 氢气 作用下， 以 乙醇 、 水 为溶剂， 70.0 ℃ 、1.4 MPa 条件下， 反应 12.0h， 生成 (S)-2-Hydroxy-4-p-tolyl-butyric acid ethyl ester
  参考文献：
  名称：

  Highly Enantioselective Sequential Hydrogenation of Ethyl 2-Oxo-4-arylbut-3-enoate to Ethyl 2-Hydroxy-4-arylbutyrate

  摘要：

  The hydrogenation of (E)-ethyl 2-oxo-4-arylbut-3-enoate with [NH2Me2](+)[{RuCl [(S)-SunPhos]}2(mu-Cl-3] gave ethyl 2-hydroxy-4-arylbutyrate with 94-96% ee. Further investigation has proved that the hydrogenation proceeded via a sequential hydrogenation of C = O and C = C bonds, which is sensitive to the reaction temperature. Hydrolysis of ethyl 2-hydroxy-4-phenylbutyrate (ee 93%) provided the 2-hydroxy-4-phenylbutyric acid with 81 % yield at 99% ee after a single recrystallization from 1, 2-dichloroethylene.

  DOI：

  10.1021/jo801140j
• 作为产物：
  描述：

  丙酮酸乙酯 在 四丁基溴化铵 、 scandium tris(trifluoromethanesulfonate) 、 1-乙基-3-甲基咪唑啉双(三氟甲基磺酰基)亚胺 作用下， 反应 9.0h， 生成 (E)-ethyl 2-oxo-4-p-tolylbut-3-enoate
  参考文献：
  名称：

  Synthesis in ionic liquids only: access to α-oxo-γ-thio-esters via Mukaiyama coupling

  摘要：

  Ionic liquids are solvents general enough to conduct a multi-step process in organic synthesis. We show that both the preparation of starting materials (thioacetals and enoxysilane) as well as their coupling can be realized in such medium. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.01.024

文献信息

• Iodine mediated a simple strategy for the synthesis of β,γ-unsaturated-α-ketoesters and its application for the synthesis of 4,5-dihydropyrazole derivatives
  作者：Anil Pommidi、Asha Begum Shaik、Anindita Chatterjee、Vijaya Laxmi Somarapu

  DOI：10.1007/s13738-020-01872-8

  日期：2020.7

  AbstractNovel and efficient method for the synthesis of a series of β,γ-unsaturated-α-ketoesters under mild conditions was developed. This one-step protocol was achieved by the reaction of electron-rich aromatic aldehydes and pyruvates in the presence of 10 mol% of molecular iodine in solvent-free condition at 80 °C temperature. A wide variety of substrates bearing electron releasing groups on aromatic

  摘要提出了在温和条件下合成一系列β，γ-不饱和α-酮酸酯的新方法。通过在80℃的温度下在无溶剂条件下，在10 mol％的分子碘存在下，富电子芳族醛与丙酮酸盐反应，可以实现这一一步操作。芳香族环上带有电子释放基团的多种底物具有良好的耐受性，并以中等至良好的产率提供了相应的β，γ-不饱和α-酮酸酯。这些β，γ-不饱和α-酮酸酯已被进一步用于合成4，5-二氢吡唑衍生物。 图形摘要
• Facile synthesis of pyrido[3,2-b]indole via multicomponent reaction strategy under aerobic conditions
  作者：Rongrong Jiang、Youming Wang、Zhenghong Zhou

  DOI：10.1016/j.tet.2016.08.050

  日期：2016.10

  developed an organocatalyzed three-component reaction of 1-acetylindolin-3-ones, β,γ-unsaturated α-ketoesters and amines, which provide an efficient approach to access polysubstituted 1H-pyrido[3,2-b]indoles. Under the catalysis of 4-methylbenzenesulfonic acid monohydrate, the reactions of a wide range of 1-acetylindolin-3-ones, β,γ-unsaturated α-ketoesters and amines took place smoothly to generate

  我们已经开发了有机物催化的1-乙酰吲哚-3-酮，β，γ-不饱和α-酮酸酯和胺的三组分反应，这为获得多取代的1 H-吡啶并[3,2- b ]吲哚提供了一种有效的方法。在4-甲基苯磺酸一水合物的催化下，各种1-乙酰吲哚-3-酮，β，γ-不饱和α-酮酸酯和胺类的反应顺利进行，生成相应的稠密取代的1 H-吡啶基[3]。在温和的反应条件下，2-2- b ]吲哚衍生物的收率可以接受。另外，以良好的产率实现了代表性产物向生物学上重要的δ-碳卤化物的进一步转化。
• Palladium-Catalyzed Asymmetric Formal [3+2] Cycloaddition of Vinyl Cyclopropanes and β,γ-Unsaturated α-Keto Esters: An Effective Route to Highly Functionalized Cyclopentanes
  作者：Liang-yong Mei、Yin Wei、Qin Xu、Min Shi

  DOI：10.1021/om300896z

  日期：2012.11.12

  Palladium-catalyzed asymmetric formal [3+2] cycloaddition of vinyl cyclopropanes and β,γ-unsaturated α-keto esters proceeded smoothly in the presence of chiral imidazoline–phosphine ligands to give the corresponding highly functionalized cyclopentanes in good yields along with high diastereo- and enantioselectivities under mild conditions.

  在手性咪唑啉-膦配体的存在下，钯催化的乙烯基环丙烷和β，γ-不饱和α-酮酯的不对称形式[3 + 2]环加成反应顺利进行，从而得到相应的高度官能化的环戊烷，并具有较高的非对映体-收率。和温和条件下的对映选择性。
• Chiral NHC-Catalyzed Oxodiene Diels−Alder Reactions with α-Chloroaldehyde Bisulfite Salts
  作者：Ming He、Brendan J. Beahm、Jeffrey W. Bode

  DOI：10.1021/ol801502h

  日期：2008.9.1

  hetero-Diels-Alder reactions with various oxodienes under biphasic reaction conditions with high levels of enantioselectivity. This new protocol makes possible enantioselective additions from commercially available chloroacetaldehyde sodium bisulfite and demonstrates that this unique class of catalysts readily tolerates aqueous conditions.

  在具有高水平对映选择性的双相反应条件下，α-氯醛亚硫酸氢盐加合物成功地用于手性 NHC 催化的杂-Diels-Alder 反应与各种氧代二烯。这种新的协议使得从市售的氯乙醛亚硫酸氢钠中进行对映选择性添加成为可能，并证明这种独特的催化剂类别很容易耐受水性条件。
• Synthesis of 5-unsubstituted dihydropyrimidinone-4-carboxylates from deep eutectic mixtures
  作者：Sangram Gore、Sundarababu Baskaran、Burkhard König

  DOI：10.3762/bjoc.18.37

  日期：——

  A facile one-pot synthesis of 5-unsubstituted dihydropyrimidinones from β,γ-unsaturated ketoesters in low melting ʟ-(+)-tartaric acid–N,N-dimethylurea mixtures is reported. This solvent-free method is very general and provides easy access to 5-unsubstituted dihydropyrimidinone-4-carboxylate derivatives in good yields.

  报道了一种简便的一锅法合成5-未取代二氢嘧啶酮，其方法是从低熔点ʟ-(+)-酒石酸-N,N-二甲基脲混合物中的β,γ-不饱和酮酯开始。这种无溶剂的方法非常通用，可轻松获得产率良好的5-未取代二氢嘧啶酮-4-羧酸酯衍生物。