(S)-ethyl 2-phenyl-2-methylmalonate | 88254-01-7

• 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: (S)-ethyl 2-phenyl-2-methylmalonate
• 英文别名: (S)-3-ethoxy-2-methyl-3-oxo-2-phenylpropanoic acid；(2S)-3-ethoxy-2-methyl-3-oxo-2-phenylpropanoic acid
• CAS: 88254-01-7
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: RDKPEKUJILTPNU-LBPRGKRZSA-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：

  (S)-ethyl 2-phenyl-2-methylmalonate 生成 2-苯基丙酸乙酯
  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：

  甲基苯基丙二酸二乙酯 在 esterase from Sulfolobus tokodaii strain 7 作用下， 以 乙腈 为溶剂， 以96%的产率得到(S)-ethyl 2-phenyl-2-methylmalonate
  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

文献信息

• Rhodium-Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide
  作者：Shingo Kawashima、Kohsuke Aikawa、Koichi Mikami

  DOI：10.1002/ejoc.201600338

  日期：2016.7

  excellent yields. In this catalytic process with carbon dioxide, intervention of the RhI–H species, which could be generated from the RhI catalyst and diethylzinc, was clarified. Significantly, the catalytic asymmetric hydrocarboxylation of α,β-unsaturated esters with carbon dioxide was also performed by employing a cationic rhodium complex possessing (S)-(–)-4,4′-bi-1,3-benzodioxole-5,5′-diylbis(diphenylphosphine)

  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。
• Enzymatic enantioselective ester hydrolysis by carboxylesterase NP
  作者：J. W. H. Smeets、A. P. G. Kieboom

  DOI：10.1002/recl.19921111104

  日期：——

  and N-arylalanine esters. The propionate esters yielded propionic acids as (S) enantiomers, whereas the alanine esters yielded the (R) enantiomers. Without a 2-aryl substituent, the enzymatic hydrolysis of the propionates occurred at a lower rate without acceptable enantioselectivity. In addition to 2-substituted propionates, only a few other esters were hydrolyzed with high enantioselectivity by carboxylesterase

  为了确定该酶的范围和局限性，已经研究了通过羧酸酯酶NP对一系列羧酸酯的酶促水解。当芳族部分是2-取代基的一部分时，以高对映选择性水解2-取代的丙酸酯。对映选择性水解可以用几种2-芳基丙酸酯，2-（芳氧基）丙酸酯和N-芳基丙氨酸酯完成。丙酸酯产生丙酸为（S）对映异构体，而丙氨酸酯产生（R）对映体。没有2-芳基取代基，丙酸酯的酶水解以较低的速率发生，而没有可接受的对映选择性。除2-取代的丙酸酯外，只有少数其他酯被羧酸酯酶NP水解而具有高对映选择性，例如一些前手性二取代丙二酸酯。1-苯基乙基乙酸酯是在酯的醇部分中具有手性的唯一底物，发现其被对映选择性地水解。
• 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。
• Improved Process for the Enantioselective Hydrolysis of Prochiral Diethyl Malonates Catalyzed by Pig Liver Esterase
  作者：Harald Gröger、Pablo Domínguez de María、Beate Kossmann、Nicole Potgrave、Stefan Buchholz、Harald Trauthwein、Oliver May

  DOI：10.1055/s-2005-871548

  日期：——

  An improved process for the enantioselective hydrolysis of prochiral 2-aryl-2-alkyl-disubstituted diethyl malonates catalyzed by pig liver esterase (PLE) was developed. With diethyl 2-phenyl-2-methylmalonate as a model substrate, the highest enantioselectivities (96% ee; /?-isomer) were achieved when carrying out the process in the presence of a suitable mixture of cosolvents (buffer-i-PrOH-t-BuOH

  开发了一种改进的方法，用于对由猪肝酯酶 (PLE) 催化的前手性 2-芳基-2-烷基-二取代丙二酸二乙酯进行对映选择性水解。使用 2-苯基-2-甲基丙二酸二乙酯作为模型底物，在合适的共溶剂混合物（缓冲液-i-PrOH- t-BuOH，8:1:1)。该过程在更高的底物浓度下也有效。该反应以多克制备规模进行，在 200 mM 的底物浓度下，转化率 > 95%，对映选择性为 96% ee，产率为 83%。
• Schneider, Manfred; Engel, Norbert; Boensmann, Heike, Angewandte Chemie, 1984, vol. 96, # 1, p. 54 - 55
  作者：Schneider, Manfred、Engel, Norbert、Boensmann, Heike

  DOI：——

  日期：——