2-oxo-4-phenyl-3-butynoic acid | 7062-59-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-oxo-4-phenyl-3-butynoic acid
• 英文别名: Phenylethynylglyoxalic acid；2-oxo-4-phenylbut-3-ynoic acid
• CAS: 7062-59-1
• 化学式: C₁₀H₆O₃
• 分子量: 174.156
• InChiKey: PLXLWOTXUMKDIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 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-4-phenyl-3-butynoic acid 在 焦磷酸硫胺素 、 柠檬酸 、 magnesium chloride 作用下， 反应 3.0h， 生成 肉桂酸
  参考文献：
  名称：

  Novel Synthesis of 2-Oxo-4-phenyl-3-butynoic Acid, a New Inhibitor and Alternate Substrate of Pyruvate Decarboxylase

  摘要：

  An improved method is reported for the synthesis of 2-oxo acids and is applied to the synthesis of 2-oxo-4-phenyl-3-butynoic acid. The compound is synthesized by reacting the N-methoxy-N-methylamide of monoethyloxalic acid with lithium phenylacetylide yielding ethyl 2-oxo-4-phenyl-3-butynoate (78% yield), followed by strictly pH-controlled hydrolysis to the free acid in nearly quantitative yield. The compound is shown to be a potent irreversible inhibitor of brewers' yeast pyruvate decarboxylase, in addition to producing both cis- and trans-cinnamic acids as products of turnover. The formation of these isomeric cinnamic acids can be rationalized if the thiamin diphosphate-bound alpha-carbanion/enamine intermediate resulting from decarboxylation is protonated at the side chain gamma carbon to form two diastereomeric allenols, whose tautomerization and hydrolysis lead to the two products.

  DOI：

  10.1021/jo00098a041
• 作为产物：
  描述：

  ethyl 2-oxo-4-phenylbut-3-ynoate 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 0.08h， 生成 2-oxo-4-phenyl-3-butynoic acid
  参考文献：
  名称：

  β，γ-炔基-α-亚氨基酯与锌（II）配合物的C-选择性和非对映选择性烷基加成

  摘要：

  由于蛋白酚α-亚氨基酯包含三个亲电中心，因此在传统合成通用手性α-氨基酸衍生物中，传统有机金属试剂的区域选择性烷基加成一直是一个严重的问题。开发了使用格利雅试剂（RMgX）衍生的锌（II）盐向α-亚氨基酯中添加不寻常的C烷基的方法。锌（II）酸盐配合物由路易斯酸性[MgX] +部分，亲核性[R 3 Zn] -部分和2 [MgX 2 ]组成。因此，离子分离的[R 3 Zn] -选择性地攻击亚氨基碳原子，该亚氨基碳原子最容易被[MgX] +的螯合活化。特别是，由于结构方面的考虑，手性β，γ-炔基-α-亚氨基酯可以强烈促进高度区域和非对映选择性的C-烷基化，并在5分钟内以高至产量。

  DOI：

  10.1002/anie.201408916

文献信息

• Divergent Synthesis of Oxepino-Phthalides and [5,5]-Oxaspirolactones through [2 + 2 + 2]- and [2 + 3]-Annulation of Alkynyl Alcohols with α-Ynone-Esters
  作者：Digambar A. Kambale、Balasaheb R. Borade、Ramavath Vinodkumar、Ravindar Kontham

  DOI：10.1021/acs.joc.3c01301

  日期：2023.9.1

  Unmasking the synthetic potential of alkyne functional group of alkynyl alcohols as surrogates of carbonyl compounds, herein we present the first Brønsted acid (TfOH)-catalyzed [2 + 2 + 2]-annulation of 4-pentyn-1-ols (possessing terminal alkyne) with α-ynone-esters to access tricyclic tetrahydro-oxepino-phthalides. Besides, an unprecedented synthesis of α-acetoaryl or α-alkynyl [5,5]-oxaspirolactones

  揭示了炔醇的炔官能团作为羰基化合物替代物的合成潜力，本文中我们提出了第一个布朗斯台德酸（TfOH）催化的 4-戊炔-1-醇（具有末端炔烃）的 [2 + 2 + 2]-环化反应)与α-炔酮-酯反应得到三环四氢氧杂苯酞。此外，通过使用 4-戊炔-1-醇（具有内部炔）作为环化配偶体，通过发散的 [2 + 3]-成环途径。
• Inactivation of the phenylpyruvate tautomerase activity of macrophage migration inhibitory factor by 2-oxo-4-phenyl-3-butynoate
  作者：Pavel A. Golubkov、William H. Johnson、Robert M. Czerwinski、Maria D. Person、Susan C. Wang、Christian P. Whitman、Marvin L. Hackert

  DOI：10.1016/j.bioorg.2006.05.001

  日期：2006.8

  Macrophage migration inhibitory factor (MIF) is an important immunoregulatory protein that has been implicated in several inflammatory diseases. MIF also has a phenylpyruvate tautomerase (PPT) activity, the role of which remains elusive in these biological activities. The acetylene compound, 2-oxo-4-phenyl-3-butynoate (2-OPB), has been synthesized and tested as a potential irreversible inhibitor of its enzymatic activity. Incubation of the compound with MIF results in the rapid and irreversible loss of the PPT activity. Mass spectral analysis established that the amino-terminal proline, previously implicated as a catalytic base in the PPT-catalyzed reaction, is the site of covalent modification. Inactivation of the PPT activity likely occurs by a Michael addition of Pro-1 to C-4 of the inhibitor. Attempts to crystallize the inactivated complex to confirm the structure of the adduct on the covalently modified Pro-1 by X-ray crystallography were not successful. Nor was it possible to unambiguously interpret electron density observed in the active sites of the native crystals soaked with the inhibitor. This may be due to crystal packing in that the side chain of Glu-16 from an adjacent trimer occupies one active site. However, this crystal contact may be partially responsible for the high-resolution quality of these MIF crystals. Nonetheless, because MIF is a member of the tautomerase superfamily, a group of structurally homologous proteins that share a beta-alpha-beta structural motif and a catalytic Pro-1, 2-OPB may find general use as a probe of tautomerase superfamily members that function as PPTs.
• Chiu Chingfan C., Jordan Frank, J. Org. Chem, 59 (1994) N 19, S 5763-5766
  作者：Chiu Chingfan C., Jordan Frank

  DOI：——

  日期：——
• US6204220B1
  申请人：——

  公开号：US6204220B1

  公开（公告）日：2001-03-20
• C-Selective and Diastereoselective Alkyl Addition to β,γ-Alkynyl-α-imino Esters with Zinc(II)ate Complexes
  作者：Manabu Hatano、Kenji Yamashita、Mai Mizuno、Orie Ito、Kazuaki Ishihara

  DOI：10.1002/anie.201408916

  日期：2015.2.23

  Since umpolung α‐imino esters contain three electrophilic centers, regioselective alkyl addition with traditional organometallic reagents has been a serious problem in the practical synthesis of versatile chiral α‐amino acid derivatives. An unusual C‐alkyl addition to α‐imino esters using a Grignard reagent (RMgX)‐derived zinc(II)ate was developed. Zinc(II)ate complexes consist of a Lewis acidic [MgX]+

  由于蛋白酚α-亚氨基酯包含三个亲电中心，因此在传统合成通用手性α-氨基酸衍生物中，传统有机金属试剂的区域选择性烷基加成一直是一个严重的问题。开发了使用格利雅试剂（RMgX）衍生的锌（II）盐向α-亚氨基酯中添加不寻常的C烷基的方法。锌（II）酸盐配合物由路易斯酸性[MgX] +部分，亲核性[R 3 Zn] -部分和2 [MgX 2 ]组成。因此，离子分离的[R 3 Zn] -选择性地攻击亚氨基碳原子，该亚氨基碳原子最容易被[MgX] +的螯合活化。特别是，由于结构方面的考虑，手性β，γ-炔基-α-亚氨基酯可以强烈促进高度区域和非对映选择性的C-烷基化，并在5分钟内以高至产量。