ethyl-2-hydroxy-3,3-dimethyl-4-oxobutanoate | 856646-71-4

• 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: ethyl-2-hydroxy-3,3-dimethyl-4-oxobutanoate
• 英文别名: 2-hydroxy-3,3-dimethyl-4-oxo-butxyric acid ethyl ester；Ethyl 2-hydroxy-3,3-dimethyl-4-oxobutanoate
• CAS: 856646-71-4
• 化学式: C₈H₁₄O₄
• 分子量: 174.197
• InChiKey: JHSNQMQCFPZPGU-UHFFFAOYSA-N

物化性质

• 沸点：
  264.4±30.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  ethyl-2-hydroxy-3,3-dimethyl-4-oxobutanoate 在 alcohol dehydrogenase 200 作用下， 以 异丙醇 为溶剂， 反应 0.5h， 以98%的产率得到
  参考文献：
  名称：

  Chemoenzymatic Synthesis of Vitamin B5-Intermediate (R)-Pantolactone via Combined Asymmetric Organo- and Biocatalysis

  摘要：

  The combination of an asymmetric organocatalytic aldol reaction with a subsequent biotransformation toward a "one-pot-like" process for the synthesis of (R)-pantolactone, which to date is industrially produced by a resolution process, is demonstrated. This process consists of an initial aldol reaction catalyzed by readily available L-histidine followed by biotransformation of the aldol adduct by an alcohol dehydrogenase without the need for intermediate isolation. Employing the industrially Attractive starting material isobutanal, a chemoenzymatic three-step process without intermediate purification is established allowing the synthesis of (R)-pantolactone in an overall yield of 55% (three steps) and high enantiomeric excess of 95%.

  DOI：

  10.1021/jo502667x
• 作为产物：
  描述：

  乙醛酸乙酯 、 异丁醇 在 N-(2-hydroxyethyl)pyrrolidine-2-carboxamide 作用下， 以 甲苯 、 叔丁醇 为溶剂， 反应 24.0h， 以84%的产率得到ethyl-2-hydroxy-3,3-dimethyl-4-oxobutanoate
  参考文献：
  名称：

  [EN] SYNTHESIS OF A RACEMIC MIXTURE OF PANTOLACTONE
  [FR] SYNTHÈSE D'UN MÉLANGE RACÉMIQUE DE PANTOLACTONE

  摘要：

  本发明涉及一种改进的合成方法，用于制备对映体混合物-泛酮内酯(I)。

  公开号：

  WO2019228873A1

文献信息

• Catalyst Repurposing Sequential Catalysis by Harnessing Regenerated Prolinamide Organocatalysts as Transfer Hydrogenation Ligands
  作者：Frederic Bourgeois、Jonathan A. Medlock、Werner Bonrath、Christof Sparr

  DOI：10.1021/acs.orglett.9b04033

  日期：2020.1.3

  A catalyst repurposing strategy based on a sequential aldol addition and transfer hydrogenation giving access to enantiomerically enriched α-hydroxy-γ-butyrolactones is described. The combination of a stereoselective, organocatalytic step, followed by an efficient catalytic aldehyde reduction induces an ensuing lactonization to provide enantioenriched butyrolactones from readily available starting

  描述了基于顺序的醛醇加成和转移氢化的催化剂再利用策略，该策略允许获得对映异构体富集的α-羟基-γ-丁内酯。立体选择性的有机催化步骤的组合，然后是有效的催化醛还原，引起随后的内酯​​化，以从容易获得的起始原料中提供对映体富集的丁内酯。通过利用脯氨酸酰胺既充当有机催化剂又充当转移加氢配体的能力，催化剂的再利用允许开发一种操作简单，经济且有效的顺序催化方法。
• Stereoselectivities of Histidine-Catalyzed Asymmetric Aldol Additions and Contrasts with Proline Catalysis: A Quantum Mechanical Analysis
  作者：Yu-hong Lam、K. N. Houk、Ulf Scheffler、Rainer Mahrwald

  DOI：10.1021/ja2118392

  日期：2012.4.11

  Quantum mechanical calculations reveal the origin of diastereo- and enantioselectivities of aldol reactions between aldehydes catalyzed by histidine, and differences between related reactions catalyzed by proline. A stereochemical model that explains both the sense and the high levels of the experimentally observed stereoselectivity is proposed. The computations suggest that both the imidazolium and the carboxylic acid functionalities of histidine are viable hydrogen-bond donors that can stabilize the cyclic aldolization transition state. The stereoselectivity is proposed to arise from minimization of gauche interactions around the forming C-C bond.