(S)-ethyl 2-hydroxy-4-oxopentanoate | 142395-25-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: (S)-ethyl 2-hydroxy-4-oxopentanoate
• 英文别名: ethyl (S)-2-hydroxy-4-oxopentanoate；ethyl (S)-2-hydroxy-4-oxovalerate；ethyl (2S)-2-hydroxy-4-oxopentanoate
• CAS: 142395-25-3
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: KMGFCSZYXHRXSL-LURJTMIESA-N

物化性质

• 沸点：
  271.3±20.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-amino-4-oxo-2-pentenoic acid ethyl ester 在 甲醇 、 4-二甲氨基吡啶 、 硫酸氢铵 、 potassium dihydrogenphosphate 、 baker's yeast 、 pig liver esterase 、 乙醇 、 葡萄糖 、 magnesium sulfate 作用下， 以 吡啶 、 水 为溶剂， 反应 72.0h， 生成 (S)-ethyl 2-hydroxy-4-oxopentanoate
  参考文献：
  名称：

  Regio - and enantioselective bioreduction of ethyl 2,4-dioxoalkanoates and γ-Keto-α-enamino esters with fermenting baker's yeast

  摘要：

  2,4-Dioxoalkanoates 1a-d and the parent compounds gamma-keto-alpha-enamino esters 2a-d are regioselectively reduced by baker's yeast to (R)-alpha-hydroxy-gamma-ketoesters 4a-d in moderate to good chemical yield and appreciable enantioselectivity. Pig liver esterase enantioselective hydrolysis of the acetyl derivatives 3a-d, easily obtained by treatment of racemic alpha-hydroxy-gamma-keto esters 4a-d, produced the optically active (S) 4a-d in good chemical (60-92%) and optical (53-92%) yield.

  DOI：

  10.1016/s0040-4039(00)78883-6

文献信息

• Asymmetric Hydrogenation of 2,4-Dioxo Esters: Selective Synthesis of 2-Hydroxy-4-oxo Esters and Direct Access to Chiral 2-Hydroxy-4-butyrolactones
  作者：Véronique Blandin、Jean-François Carpentier、André Mortreux

  DOI：10.1002/(sici)1099-0690(199908)1999:8<1787::aid-ejoc1787>3.0.co;2-o

  日期：1999.8

  2,4-Dioxoesters 1a–c are selectively converted into optically active 2-hydroxy-4-oxoesters 2a–c by hydrogenation with chiral rhodium-aminophosphane-phosphinite catalysts (82–88% ee) or ruthenium-bisphosphane catalysts (52–67% ee). Direct one-pot hydrogenation of 2,4-dioxoesters 1a–c to 2-hydroxy-4-butyrolactones 4a–c proceeds in high yields; catalytic activities, chemo-, dia-, and enantioselectivities

  2,4-二氧代酯 1a-c 通过手性铑-氨基膦-次膦酸催化剂（82-88% ee）或钌-双膦催化剂（52-67）的氢化反应选择性地转化为光学活性的 2-羟基-4-氧代酯 2a-c % ee）。2,4-二氧代酯 1a-c 直接一锅加氢生成 2-羟基-4-丁内酯 4a-c，收率高；催化活性、化学选择性、渗析选择性和对映选择性在很大程度上取决于底物和催化剂的性质。
• Heterogeneous Enantioselective Hydrogenation of Activated Ketones Catalyzed by Modified Pt‐Catalysts: A Systematic Structure‐Selectivity Study
  作者：Christian Exner、Andreas Pfaltz、Martin Studer、Hans‐Ulrich Blaser

  DOI：10.1002/adsc.200303104

  日期：2003.11

  1–5 and 8, all carrying an sp3 carbon next to the keto group) or toluene (6 and 7, with an sp2 carbon next to the ketone). The presence and nature of the substituent R' at the quinuclidine significantly affected the ee (positive and negative effects). Certain combinations of an aromatic system and an amino function were preferred: For the quinuclidine moiety, quinoline and to a somewhat lesser extent

  进行了系统的结构选择性研究，用手性改性的Pt / Al 2 O 3催化剂对活化的酮进行对映选择性加氢。为此，有18种改性剂，它们含有能与Pt表面形成强吸附复合物的扩展的芳族体系，以及合适的具有氨基官能团的手性基团，能够与底物的酮基相互作用（HCd，Qd，HCn，Qn在标准条件下，在AcOH和甲苯中的8种不同的活化酮上制备并测试了半合成衍生物以及合成类似物。发现底物和/或改性剂结构的相对较小的结构变化强烈影响对映选择性，并且对于所有底物都不存在“最佳”改性剂。在组合奎宁环衍生的改性剂与萘或喹啉环，获得对于所有底物的最高EES，无论是在AcOH（基板1 - 5和8中，所有承载SP 3旁边碳酮基）或甲苯（6和7，带有sp 2碳旁边的酮）。奎宁环上取代基R'的存在和性质显着影响ee（正效应和负效应）。优选芳族体系和氨基官能团的某些组合：对于喹核苷部分，喹啉和程度较小的萘是更好的匹配，而对于吡咯烷基
• Hydrogen Bond Catalyzed Enantioselective Vinylogous Mukaiyama Aldol Reaction
  作者：Vijaya Bhasker Gondi、Michel Gravel、Viresh H. Rawal

  DOI：10.1021/ol052301p

  日期：2005.12.1

  [chemical reaction: see text]. The concept of hydrogen bonding catalysis was extended to the vinylogous Mukaiyama aldol reaction, which gives rapid access to polyketide derivatives. The reaction of the silyldienol ether shown and a range of aldehydes catalyzed by TADDOL proceeds regiospecifically to produce the addition products in good yields and enantiomeric excesses.

  [化学反应：见正文]。氢键催化的概念扩展到乙烯基类的Mukaiyama aldol反应，该反应可快速获得聚酮化合物衍生物。所示的甲硅烷基二烯醇醚与TADDOL催化的一系列醛的反应在区域上特异性地进行，从而以高收率和对映体过量产生加成产物。
• Organocatalytic Enantioselective Synthesis of Secondary α-Hydroxy­carboxylates
  作者：Cong-Gui Zhao、Rajasekhar Dodda

  DOI：10.1055/s-2007-982552

  日期：2007.6

  Enantioenriched secondary α-hydroxycarboxylates have been synthesized in good yields and enantioselectivities by using the cross-aldol reaction of ketones and ethyl glyoxylate with a ­proline-derived dipeptide as the catalyst.

  以脯氨酸衍生二肽为催化剂，通过酮和乙醛酸乙酯的交叉醛醇反应，合成了对映体丰富的仲δ-羟基羧酸酯，并获得了良好的产率和对映体选择性。
• Enantio- and chemoselective reduction of 2,4-diketo acid derivatives with cinchona modified Pt-catalyst—Synthesis of (R)-2-hydroxy-4-phenylbutyric acid ethyl ester
  作者：Martin Studer、Stefan Burkhardt、Adriano F. Indolese、Hans-Ulrich Blaser

  DOI：10.1039/b002538k

  日期：——

  The enantio- and chemoselective hydrogenation of several 2,4-diketo acid derivatives to the corresponding 2-hydroxy compounds with cinchona modified Pt catalysts can be carried out with chemoselectivities of >99% and enantioselectivities up to 86% (R) and 68% (S), respectively, and enrichment to >98% ee was possible for several compounds by one crystallization, opening up an efficient technical synthesis of (R)-2-hydroxy-4-phenylbutyric acid ethyl ester, a building block for several ACE inhibitors.

  在金鸡纳改性铂催化剂的作用下，多种 2,4-二酮酸衍生物可以对映和化学选择性氢化为相应的 2-羟基化合物，化学选择性大于 99%，对映选择性分别高达 86%（R）和 68%（S）、通过一次结晶，几种化合物的对映体选择性可富集到 >98% ee，从而开辟了(R)-2-羟基-4-苯基丁酸乙酯的高效技术合成途径，而(R)-2-羟基-4-苯基丁酸乙酯是几种 ACE 抑制剂的基本成分。