2-oxo-pent-3t-enoic acid | 68982-84-3

• 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: 2-oxo-pent-3t-enoic acid
• 英文别名: 2-Oxo-pent-3t-ensaeure；2-Keto-3-pentensaeure；(E)-2-oxopent-3-enoic acid
• CAS: 68982-84-3
• 化学式: C₅H₆O₃
• 分子量: 114.101
• InChiKey: IWARWSDDJHGZOW-NSCUHMNNSA-N

物化性质

• 沸点：
  183.4±13.0 °C(Predicted)
• 密度：
  1.183±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-oxo-pent-3t-enoic acid 在 苄基紫精 氢气 作用下， 以 水 为溶剂， 35.0 ℃ 、101.32 kPa 条件下， 以90%的产率得到(R)-(E)-2-hydroxy-3-pentenoic acid
  参考文献：
  名称：

  通过用氢气或甲酸盐还原2-羟肟酸和寻常变形杆菌的多官能团（）-2-羟基羧酸

  摘要：

  各种（）-2-羟基酸如（）-2-羟基-3-烯酸，3,5-二烯酸，4-氧代，（）-3-羟基等，其制备规模可达到通过以寻常的毕赤酵母和氢气和/或甲酸作为电子给体，对相应的2-氧代酸进行生物催化还原，可得到0.12摩尔。除2-羟基-4-氧代酸外，可以证明对映体过量> 97％。对于4-氧代衍生物，可以假定该对映体过量。分离出的产物的产率很高，因为它们是从相当少量的生物催化剂中分离出来的，并且缓冲液的浓度很低，获得的产物浓度在0.1–0.24 M的范围内。在15–20小时内形成1 mmol的产品，约20–40 mg（干重）寻常型毕赤酵母 单元格是必需的。

  DOI：

  10.1016/s0040-4020(01)86506-6
• 作为产物：
  描述：

  (E)-ethyl 2-oxo-3-pentenoate 在 氢氧化钾 作用下， 以 水 为溶剂， 反应 15.0h， 生成 2-oxo-pent-3t-enoic acid
  参考文献：
  名称：

  通过用氢气或甲酸盐还原2-羟肟酸和寻常变形杆菌的多官能团（）-2-羟基羧酸

  摘要：

  各种（）-2-羟基酸如（）-2-羟基-3-烯酸，3,5-二烯酸，4-氧代，（）-3-羟基等，其制备规模可达到通过以寻常的毕赤酵母和氢气和/或甲酸作为电子给体，对相应的2-氧代酸进行生物催化还原，可得到0.12摩尔。除2-羟基-4-氧代酸外，可以证明对映体过量> 97％。对于4-氧代衍生物，可以假定该对映体过量。分离出的产物的产率很高，因为它们是从相当少量的生物催化剂中分离出来的，并且缓冲液的浓度很低，获得的产物浓度在0.1–0.24 M的范围内。在15–20小时内形成1 mmol的产品，约20–40 mg（干重）寻常型毕赤酵母 单元格是必需的。

  DOI：

  10.1016/s0040-4020(01)86506-6

文献信息

• Ketonization of 2-hydroxy-2,4-pentadienoate by 4-oxalocrotonate tautomerase: implications for the stereochemical course and the mechanism
  作者：Huiling Lian、Christian P. Whitman

  DOI：10.1021/ja00071a007

  日期：1993.9

  4-Oxalocrotonate tautomerase (EC 5.3.2-; 4-OT), an enzyme involved in the bacterial degradation of catechol to intermediates in the Krebs cycle, catalyzes the ketonization of 2-hydroxymuconate (1) to the α,β-unsaturated ketone (E)-2-oxo-3-hexenedioate (2). Kinetic studies on 4-OT suggest that the enzyme is an isomerase and catalyzes the transformation of (E)-2-oxo-4-hexenedioate (3) to 2 through the

  4-草酰巴豆酸互变异构酶 (EC 5.3.2-; 4-OT)，一种参与将儿茶酚细菌降解为克雷布斯循环中间体的酶，催化 2-羟基粘康酸 (1) 酮化为 α,β-不饱和酮(E)-2-oxo-3-hexenedioate (2)。对 4-OT 的动力学研究表明，该酶是一种异构酶，通过 1 的中介催化 (E)-2-oxo-4-hexenedioate (3) 转化为 2。异构酶可以通过 «one-base » 或“双基”机制。异构酶反应的整体立体化学过程可用于区分这两种机制。4-OT 反应的立体化学分析存在挑战，因为所提出的底物 3 无法合成或分离
• Yamanishi; Obata, Nippon Nogeikagaku Kaishi, 1953, vol. 27, p. 657
  作者：Yamanishi、Obata

  DOI：——

  日期：——
• Pollard, John R.; Henderson, Ian M. J.; Bugg, Timothy D. H., Chemical Communications, 1997, # 19, p. 1885 - 1886
  作者：Pollard, John R.、Henderson, Ian M. J.、Bugg, Timothy D. H.

  DOI：——

  日期：——
• The Contribution of the Substrate's Carboxylate Group to the Mechanism of 4-Oxalocrotonate Tautomerase
  作者：Huiling Lian、Robert M. Czerwinski、Thanuja M. Stanley、William H. Johnson、Robert J. Watson、Christian P. Whitman

  DOI：10.1006/bioo.1998.1095

  日期：1998.10

  4-Oxalocrotonate tautomerase (4-OT) converts 2-oxo-4E-hexenedioate (1) to 2-oxo-3E-hexenedioate (3) through the dienol intermediate, 2-hydroxy-2,4-hexadiene-1,6-dioate (2). Previous studies established that the isomerization of 1 to 3 is primarily a suprafacial process. It was also suggested that the 6-carboxylate group of the substrate maintains the regio- and stereochemical fidelity of the reaction by anchoring the substrate at the active site. A subsequent study suggested an additional role for the 6-carboxylate group in the mechanism: the enzyme may utilize the binding energy of the carboxylate group to facilitate catalysis. In order to explore the role of the carboxylate group in the mechanism further, the nonenzymatic rate constants for mono- and dicarboxylated substrates were measured and compared to the rates obtained for the corresponding enzymatic reactions. The results show that the missing carboxylate group has a profound effect on enzymatic catalysis as evidenced by the significant decreases (a 10(4)- and a 10(5)-fold reduction) in the values of k(cat)/K-m observed for the two monocarboxylated substrates. A comparison of the nonenzymatic rate constants indicates that the reduced k(cat)/K-m values cannot be explained on the basis of the chemical reactivities. The stereochemical course of the 4-OT-catalyzed reaction was also determined using 2-hydroxy-2,4Z-heptadiene-1,7-dioate. The stereochemical analysis reveals that the presence of the carboxylate group improves the stereoselectivity of the enzyme-catalyzed ketonization of 2-hydroxy-2,4Z-heptadiene-1,7-dioate to 2-oxo-[3-H-2]-4Z-heptene-1,7-dioate in (H2O)-H-2-a result that is consistent with its previously assigned role. These findings provide further evidence that the substrate's carboxylate group contributes to the mechanism of the enzyme in two ways: it anchors the substrate at the active site and it facilitates catalysis by destabilizing the substrate or by stabilizing the transition state. (C) 1998 Academic Press.
• Polyfunctional ()-2-hydroxycarboxylic acids by reduction of 2-oxo acids with hydrogen gas or formate and resting cells of proteus vulgaris
  作者：Anita Schummer、Hongtao Yu、Helmut Simon

  DOI：10.1016/s0040-4020(01)86506-6

  日期：1991.11

  Various ()-2-hydroxy acids such as ()-2-hydroxy-3-enoic-, 3,5-dienoic-, 4-oxo-, ()-3-hydroxy and some others were prepared on a scale up to 0.12 mol by biocatalytic reduction of the corresponding 2-oxo acids with P. vulgaris and hydrogen gas and/or formate as electron donors. With the exception of the 2-hydroxy-4-oxo acids it could be proved that the enantiomeric excess is > 97%. For the 4-oxo derivatives

  各种（）-2-羟基酸如（）-2-羟基-3-烯酸，3,5-二烯酸，4-氧代，（）-3-羟基等，其制备规模可达到通过以寻常的毕赤酵母和氢气和/或甲酸作为电子给体，对相应的2-氧代酸进行生物催化还原，可得到0.12摩尔。除2-羟基-4-氧代酸外，可以证明对映体过量> 97％。对于4-氧代衍生物，可以假定该对映体过量。分离出的产物的产率很高，因为它们是从相当少量的生物催化剂中分离出来的，并且缓冲液的浓度很低，获得的产物浓度在0.1–0.24 M的范围内。在15–20小时内形成1 mmol的产品，约20–40 mg（干重）寻常型毕赤酵母 单元格是必需的。