2-hydroxy-2,4-pentadienoate | 167318-99-2

• 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-hydroxy-2,4-pentadienoate
• 英文别名: 2-hydroxypentadienoic acid；2-hydroxy-2,4-pentadienoic acid；(2Z)-2-hydroxypenta-2,4-dienoic acid
• CAS: 167318-99-2
• 化学式: C₅H₆O₃
• 分子量: 114.101
• InChiKey: VHTQQDXPNUTMNB-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-hydroxy-2,4-pentadienoate 在 2-oxopent-4-enoate hydratase 锰 作用下， 生成 4-Hydroxy-2-oxopentanoic acid
  参考文献：
  名称：

  Pollard, John R.; Henderson, Ian M. J.; Bugg, Timothy D. H., Chemical Communications, 1997, # 19, p. 1885 - 1886

  摘要：

  DOI：
• 作为产物：
  描述：

  (2Z,4E)-2-hydroxy-6-oxonona-2,4-dienedioic acid 在 potassium phosphate buffer 作用下， 反应 0.08h， 生成 2-hydroxy-2,4-pentadienoate
  参考文献：
  名称：

  Chemistry of extradiol aromatic ring cleavage: isolation of a stable dienol ring fission intermediate and stereochemistry of its enzymatic hydrolytic clevage

  摘要：

  苯丙酸代谢途径中的元环裂解中间体以稳定的反式二烯醇形式存在；水解酶 MhpC 在分解该中间体时，会用来自水中的质子全面取代琥珀酰基，并保留立体化学结构。

  DOI：

  10.1039/c39940001163

文献信息

• Synthetic 6-aryl-2-hydroxy-6-ketohexa-2,4-dienoic acid substrates for C–C hydrolase BphD: investigation of a general base catalytic mechanism
  作者：Damian M. Speare、Sarah M. Fleming、Martin N. Beckett、Jian-Jun Li、Timothy D. H. Bugg

  DOI：10.1039/b410322j

  日期：——

  synthetic ring fission intermediates were used to investigate the enzymatic reaction catalysed by C-C hydrolase BphD from Pseudomonas LB400. A reduced substrate analogue 2,6-dihydroxy-6-phenylhexa-2,4-dienoic acid was processed enzymatically to benzaldehyde by C-C hydrolase BphD, consistent with a catalytic mechanism involving general base-catalysed attack of water to give a gem-diol intermediate, and not

  使用Heck偶联策略，已建立了细菌羟基裂解途径上的2-羟基-6-酮己二-2,4-二烯酸中间体的化学合成方法。3-溴-2-乙酰氧基丙烯酸乙酯与1-芳基乙烯基缩酮或1-芳基烯丙基醇的偶联以70-90％的收率进行。与烷基乙烯基缩酮的Heck偶联也是成功的，从而允许合成烷基取代的环裂变中间体。合成的环裂变中间体用于研究假单胞菌LB400的CC水解酶BphD催化的酶促反应。通过CC水解酶BphD将还原的底物类似物2,6-二羟基-6-苯基六-2,4-二烯酸酶解为苯甲醛，这与涉及一般碱催化的水攻击产生宝石-二醇中间体的催化机理相一致。 ，且与亲核机制不一致。针对BphD测定了一系列对位取代的2-羟基-6-酮-6-苯基六-2,4-二烯酸底物，推导的Hammett图（rho = -0.71）与过渡中离去的碳负离子一致CC裂解状态。
• 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
• Stereochemistry of the reaction catalysed by 2-hydroxy-6-keto-6-phenyl-hexa-2,4-dienoic acid 5,6-hydrolase (BphD)
  作者：Jian-Jun Li、Timothy D. H. Bugg

  DOI：10.1039/b415491f

  日期：——

  The stereochemical course of the reaction catalysed by C-C hydrolase BphD from Burkholderia xenovorans LB400 occurs with replacement of a benzoyl group by hydrogen with overall retention of stereochemistry.

  CC水解酶BphD催化来自异种伯克霍尔德氏菌LB400催化的反应的立体化学过程是通过用氢置换苯甲酰基而完全保留了立体化学而发生的。
• Mechanism of Extradiol Catechol Dioxygenases: Evidence for a Lactone Intermediate in the 2,3-Dihydroxyphenylpropionate 1,2-Dioxygenase Reaction
  作者：Jonathan Sanvoisin、G. John Langley、Timothy D. H. Bugg

  DOI：10.1021/ja00134a041

  日期：1995.7
• 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.