(+)-2-(3-oxo-1-phenylbutyl)malonic acid diethyl ester

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (+)-2-(3-oxo-1-phenylbutyl)malonic acid diethyl ester
• 英文别名: (S)-2-(3-oxo-1-phenylbutyl)malonic acid diethyl ester；diethyl 2-((S)-3-oxo-1-phenylbutyl)malonate；(S)-diethyl 2-(3-oxo-1-phenylbutyl)malonate；(S)-4-[bis(ethoxycarbonyl)methyl]-4-phenyl-2-butanone；diethyl 2-[(1S)-3-oxo-1-phenylbutyl]propanedioate
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: JGHPGLZZAXUIJE-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  苄叉丙酮 、 丙二酸二乙酯 在 [2alpha-Aminocyclohexane-1beta-ylamino[3,5-bis(trifluoromethyl)benzylamino]methylene]malononitrile 、 苯甲酸 作用下， 以 neat (no solvent) 为溶剂， 反应 94.0h， 以97%的产率得到(+)-2-(3-oxo-1-phenylbutyl)malonic acid diethyl ester
  参考文献：
  名称：

  使用二氨基亚甲基丙二腈有机催化剂将丙二酸酯无溶剂的不对称共轭加成

  摘要：

  二氨基亚甲基丙二腈有机催化剂1可以有效地促进丙二酸酯向α，β-不饱和酮的不对称共轭加成，从而以高达98％ee的高产率提供相应的加成产物。

  DOI：

  10.1016/j.tetlet.2014.05.100

文献信息

• Asymmetric Michael Addition of Malonates to Enones Catalyzed by a Primary β-Amino Acid and Its Lithium Salt
  作者：Masanori Yoshida、Mao Narita、Shoji Hara

  DOI：10.1021/jo201429w

  日期：2011.10.21

  Highly enantioselective Michael addition of malonates to enones was achieved using a mixed catalyst consisting of a primary β-amino acid, O-TBDPS (S)-β-homoserine, and its lithium salt. Various cyclic and acyclic enones were converted into 1,5-ketoesters in high yields (up to 92%) with high enantioselectivity (up to 97% ee) under mild reaction conditions. Details of synthesis of the catalyst, optimization

  使用由伯β-氨基酸，O - TBDPS（S）-β-高丝氨酸及其锂盐组成的混合催化剂，实现了丙二酸酯向烯酮的高度对映选择性迈克尔加成。在温和的反应条件下，各种环状和无环烯酮以高对映选择性（高达97％ee）高收率（高达92％）转化为1,5-酮酸酯。描述了催化剂的合成，迈克尔加成反应的反应条件的优化以及合理的反应机理的细节。
• Asymmetric organocatalytic conjugate addition of malonates to enones using a proline tetrazole catalyst
  作者：Kristian Rahbek Knudsen、Claire E. T. Mitchell、Steven V. Ley

  DOI：10.1039/b514636d

  日期：——

  5-Pyrrolidin-2-yltetrazole performs as a useful organocatalyst for the asymmetric addition of malonates to a range of enones, with good to excellent enantioselectivities.

  5-吡咯烷-2-基四唑作为有用的有机催化剂，用于丙二酸酯不对称加成到一系列烯酮中，具有良好的至优异的对映选择性。
• Enantioselective Organocatalytic Michael Addition of Malonates to α,β-Unsaturated Ketones
  作者：Pengfei Li、Shigang Wen、Feng Yu、Qiaoxia Liu、Wenjun Li、Yongcan Wang、Xinmiao Liang、Jinxing Ye

  DOI：10.1021/ol802892h

  日期：2009.2.5

  derived from 1,2-diaminocyclohexane and 9-amino (9-deoxy) cinchona alkaloid was developed into asymmetric Michael addition of malonates to enones. A series of cyclic and acyclic enones could react very well with different malonates in the presence of 4 with 0.5−10 mol % catalyst loading affording chiral Michael adducts with excellent yields and ee values.

  由1,2-二氨基环己烷和9-氨基（9-脱氧）金鸡纳生物碱衍生的新型伯胺硫脲有机催化剂被开发为丙二酸酯向烯酮的不对称迈克尔加成反应。一系列环状和无环烯酮在4的存在下，催化剂负载量为0.5-10 mol％，可以与不同的丙二酸酯很好地反应，从而提供具有优异收率和ee值的手性迈克尔加合物。
• Highly Efficient Asymmetric Michael Addition Reaction of Malonates to α,β-Unsaturated Ketones Promoted by a Chiral Thiourea/PPY Dual-Catalyst System
  作者：Hiyoshizo Kotsuki、Maya Moritaka、Naomu Miyamae、Keiji Nakano、Yoshiyasu Ichikawa

  DOI：10.1055/s-0032-1317317

  日期：——

  The enantioselective Michael addition reaction of malonates to α,β-unsaturated ketones is efficiently promoted by a combined dual-catalyst system composed of chiral thiourea and 4-pyrrolidinopyridine (PPY) in toluene. The expected Michael adducts with cyclic and acyclic enones are obtained in excellent yields and with excellent enantioselectivities.

  由手性硫脲和 4-吡咯烷吡啶 (PPY) 在甲苯中组成的组合双催化剂体系有效地促进了丙二酸酯与 α,β-不饱和酮的对映选择性迈克尔加成反应。预期的具有环状和无环烯酮的迈克尔加合物以优异的产率和优异的对映选择性获得。
• A New Microwave-Assisted Organocatalytic Solvent-Free Synthesis of Optically Enriched Michael Adducts
  作者：Antonio Procopio、Antonio De  Nino、Monica Nardi、Manuela Oliverio、Rossella Paonessa、Raffaele Pasceri

  DOI：10.1055/s-0030-1258126

  日期：2010.7

  A high-yielding reaction protocol for the microwave-assisted organocatalytic conjugate addition of diethyl malonate to enones under solvent-free conditions is proposed. The method still permits the use of cheap and commercially available L -proline furnishing very good performance at least in the case of 1-alkyl-3-monosubstituted enones.

  提出了一种在无溶剂条件下将丙二酸二乙酯与烯酮进行微波辅助有机催化共轭加成的高产反应方案。该方法仍然允许使用廉价且可商购的L-脯氨酸，至少在1-烷基-3-单取代烯酮的情况下提供非常好的性能。