Methylphenylmalonic acid monoethyl ester | 62707-19-1

• 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: Methylphenylmalonic acid monoethyl ester
• 英文别名: 3-ethoxy-2-methyl-3-oxo-2-phenylpropanoic acid；Phenyl methyl malonic acid ethyl ester
• CAS: 62707-19-1
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: RDKPEKUJILTPNU-UHFFFAOYSA-N

物化性质

• 沸点：
  346.1±30.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methylphenylmalonic acid monoethyl ester 在 esterase from Sulfolobus tokodaii strain 7 作用下， 以 乙腈 为溶剂， 生成 2-methyl-2-phenylmalonic acid
  参考文献：
  名称：

  Thermally driven asymmetric domino reaction catalyzed by a thermostable esterase and its variants

  摘要：

  We have developed a thermally driven domino reaction for the synthesis of (S)-alpha-arylpropionates (profens) using a thermostable esterase from Sulfolobus tokodaii strain 7. Stereoselectivity was improved considerably by engineering of the active site. Stereoselective decarboxylation at the active site of an esterase is a new reaction for the synthesis of optically active carboxylic acids. Crown Copyright (c) 2013 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.01.080
• 作为产物：
  描述：

  2-苯基丙烯酸 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 氯化亚砜 、 diethylzinc 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 Methylphenylmalonic acid monoethyl ester
  参考文献：
  名称：

  铑催化烯烃与二氧化碳的加氢羧化反应

  摘要：

  探索了在空气稳定的铑催化剂存在下，苯乙烯衍生物和 α,β-不饱和羰基化合物与 CO2 (101.3 kPa) 的催化加氢羧化反应。[RhCl(cod)]2 (cod = cyclooctadiene) 作为催化剂和二乙基锌作为氢化物源的组合允许有效的加氢羧化并以中等至极好的产率提供相应的α-芳基羧酸。在这个使用二氧化碳的催化过程中，可以从 RhI 催化剂和二乙基锌产生的 RhI-H 物种的干预得到澄清。值得注意的是，α,β-不饱和酯与二氧化碳的催化不对称加氢羧化反应也通过使用含有 (S)-(-)-4,4'-bi-1,3-benzodioxole-5 的阳离子铑络合物进行，5'-二基双（二苯基膦）[(S)-SEGPHOS] 作为手性二膦配体。通过确定产品的绝对构型，提出了一个合理的不对称归纳模型。

  DOI：

  10.1002/ejoc.201600338

文献信息

• Environmentally benign metal-free decarboxylative aldol and Mannich reactions
  作者：Jérôme Baudoux、Pierre Lefebvre、Rémi Legay、Marie-Claire Lasne、Jacques Rouden

  DOI：10.1039/b915681j

  日期：——

  hemimalonate used. With the unsubstituted substrate, a carboxylic acid intermediate was isolated upon acid quench resulting from the nucleophilic addition of the putative enol carboxylate anion of the hemimalonate to imines/aldehydes before CO2 loss. With substituted hemimalonates, the reaction likely involved an enolate which then added to imines/aldehydes or was competitively protonated. According to the base

  旨在发展绿色和高效的C–C键结构（醛醇盐和 曼尼希反应）的脱羧亲核加成 丙二酸 一半 酯 到 亚胺研究了在无金属的温和条件下的醛或醛。温度的仔细控制和有机碱的适当的选择使我们能够得到β氨基酯或β羟基酯，包括在中等至良好的产率α取代和α，α-二取代的。1 H NMR 对反应的监测揭示了两种不同的机制，具体取决于 半棉酸盐用过的。对于未取代的底物，羧酸 酸淬灭后分离出中间体，归因于亲核加成 烯醇 羧酸盐 的负离子 半棉酸盐 到 亚胺/醛在CO 2损失之前。对于取代的半棉酸酯，反应可能涉及烯醇，然后将其添加到亚胺/醛或竞争性质子化。根据所用的碱，该反应可以在以下条件下进行溶剂 自由条件或在温和条件下的离子液体中。
• Computational and Experimental Insights into Asymmetric Rh‐Catalyzed Hydrocarboxylation with CO ₂
  作者：Ljiljana Pavlovic、Martin Pettersen、Ashot Gevorgyan、Janakiram Vaitla、Annette Bayer、Kathrin H. Hopmann

  DOI：10.1002/ejoc.202001469

  日期：2021.1.26

  Computational and experimental methods were employed to study the potential of different bidentate ligands in the enantioselective Rh‐catalyzed hydrocarboxylation of acrylates. Our computational analysis shows that during C−C bond formation, CO2 prefers an outer sphere insertion mode. The ligands StackPhos and tBu‐BOX show good yields and display an intriguing stacking interaction between the internal

  采用计算和实验方法研究了不同双齿配体在丙烯酸对映选择性Rh催化加氢羧化反应中的潜力。我们的计算分析表明，在C-C键形成期间，CO 2倾向于外球插入模式。配体StackPhos和t Bu‐BOX表现出良好的收率，并且在内部N杂环与CO 2之间表现出令人感兴趣的堆积相互作用。
• MALONATE DECARBOXYLASES FOR INDUSTRIAL APPLICATIONS
  申请人：Hauer Bernhard

  公开号：US20100311037A1

  公开（公告）日：2010-12-09

  The present invention relates to a method for the enzymatic decarboxylation of malonic acid (propanedioic acid) derivatives catalyzed by enzymes structurally and/or functionally related to arylmalonate decarboxylase (AMDase) as isolated from microorganisms of the genus Bordetella . The present invention also relates to novel enzymes with a decarboxylase activity, useful for performing the claimed method, mutants thereof, corresponding coding sequences and expression systems, methods of preparing said novel enzymes, and screening methods for obtaining further suitable enzymes also having said decarboxylase activity.

  本发明涉及一种利用结构和/或功能与芳基丙二酸脱羧酶（AMDase）相关的酶催化菌属Bordetella微生物中分离的方法，对丙二酸（丙二酸）衍生物进行酶促脱羧的方法。本发明还涉及具有脱羧酶活性的新酶，用于执行所述方法的突变体，相应的编码序列和表达系统，制备所述新酶的方法以及用于获得具有所述脱羧酶活性的进一步合适酶的筛选方法。
• New malonate decarboxylases for industrial applications
  申请人：BASF SE

  公开号：EP2065470A1

  公开（公告）日：2009-06-03

  The present invention relates to a method for the enzymatic decarboxylation of aryl-substituted malonic acid (propanedioic acid) derivatives catalyzed by enzymes structurally and/or functionally related to arylmalonate decarboxylase (AMDase) as isolated from microorganisms of the genus Bordetella. The present invention also relates to novel enzymes with arylmalonate decarboxylase activity, useful for performing the claimed method, mutants thereof, corresponding coding sequences and expression systems, methods of preparing said novel enzymes, and screening methods for obtaining further suitable enzymes also having said arylmalonate decarboxylase activity.

  本发明涉及一种芳基取代丙二酸(丙二酸)衍生物的酶促脱羧方法，该方法由从博德特氏菌属微生物中分离出来的在结构上和/或功能上与芳基丙二酸脱羧酶(AMDase)有关的酶催化。本发明还涉及具有芳基丙二酸脱羧酶活性的新型酶，这种酶对实施所要求的方法有用，本发明还涉及其突变体、相应的编码序列和表达系统、制备所述新型酶的方法，以及获得同样具有所述芳基丙二酸脱羧酶活性的其他合适酶的筛选方法。
• Enantioselective catalysis, C. Decarboxylation of malonic acids in the presence of copper(I) compounds ? Not a copper(I) catalysis but a base effect
  作者：H. Brunner、J. M�ller、J. Spitzer

  DOI：10.1007/bf00807023

  日期：——

  The catalytic decarboxylation of malonic acids, claimed to be catalyzed by copper(I) compounds, has been investigated. Decarboxylation of different malonic acid derivatives (1-5) in acetonitrile was far more effective with Cu2O than with CuCl. Thus, the decarboxylation is obviously influenced by the basicity of the anion. In the decarboxylation of phenylmalonic acid (3), bis(tricyclohexylphosphane)copper(I) hydrogenphenylmalonate (6) and potassium hydrogenphenylmalonate (7) show nearly identical rate constants. It is concluded that the monoanions of the malonic acid derivatives are the reactive species undergoing decarboxylation. Further experiments are presented which demonstrate that everything that increases the concentration of the monoanions also increases the rate of decarboxylation. In the enantioselective decarboxylation of the monoethyl ester of methylphenylmalonic acid (2), the enantiomeric excess of (S)-(+)-ethyl 2-phenylpropionate could be raised to 34.5% ee using the alkaloid cinchonine.