ethyl 4-(p-chlorophenyl)-2-oxo-3-butynoate

• 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: ethyl 4-(p-chlorophenyl)-2-oxo-3-butynoate
• 英文别名: ethyl 4-(4-chlorophenyl)-2-oxobut-3-ynoate
• 化学式: C₁₂H₉ClO₃
• 分子量: 236.655
• InChiKey: KZOUKEJFODTFHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 4-(p-chlorophenyl)-2-oxo-3-butynoate 在 三苯基膦 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 7.0h， 生成 ethyl 4-(4-chlorophenyl)-2-(ethyl(4-methoxyphenyl)amino)-5-oxohexa-2,3-dienoate
  参考文献：
  名称：

  Regioselective Tandem N-Alkylation/C-Acylation of β,γ-Alkynyl α-Imino Esters

  摘要：

  A new synthesis of alpha-quaternary alkynyl amino esters and allenoates was developed utilizing umpolung N-addition to beta,gamma-alkynyl alpha-imino esters followed by regioselective acylation. The reaction exhibits broad substrate generality and unique regioselectivity. Moreover, synthesis of alpha-quaternary alkynyl amino esters was also carried out via oxidation of the intermediary enolate followed by alkylation.

  DOI：

  10.1021/ol401934x
• 作为产物：
  描述：

  4-氯苯乙炔 、 2-(n-甲氧基-n-甲基氨基)-2-氧代乙酸乙酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以66%的产率得到ethyl 4-(p-chlorophenyl)-2-oxo-3-butynoate
  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

文献信息

• Synthesis of α-(4-Oxazolyl)amino Esters via Brønsted Acid Catalyzed Tandem Reaction
  作者：Ansoo Lee、Seohee Oh、Hyunwoo Kim

  DOI：10.1021/acs.orglett.8b01212

  日期：2018.6.1

  A one-step, Brønsted acid catalyzed tandem reaction for the synthesis of α-(4-oxazolyl)amino esters was developed. 4-Nitrobenzenesulfonic acid was found to be an efficient catalyst for the coupling of ethyl 2-oxobut-3-ynoates with amides to provide various α-(4-oxazolyl)amino esters. The experimental and X-ray crystallographic data suggest that a series of bond-forming reactions including imine formation

  开发了一步一步布朗斯台德酸催化串联反应合成α-（4-恶唑基）氨基酯的方法。发现4-硝基苯磺酸是使2-氧代丁-3-炔酸乙酯与酰胺偶联以提供各种α-（4-恶唑基）氨基酯的有效催化剂。实验和X射线晶体学数据表明，包括亚胺形成，分子间迈克尔加成和分子内迈克尔加成在内的一系列成键反应涉及生成恶唑和氨基酸官能团。
• Organocatalytic Asymmetric Dearomatization Reaction for the Synthesis of Axial Chiral Allene-Derived Naphthalenones Bearing Quaternary Stereocenters
  作者：Alemayehu Gashaw Woldegiorgis、Zhao Han、Xufeng Lin

  DOI：10.1021/acs.orglett.1c01849

  日期：2021.9.3

  γ-alkynyl-α-imino esters with complete atom economy is disclosed via chiral phosphoric acid catalysis. This protocol provides facile and efficient access to asymmetric construction of a broad range of axially chiral allene-derived naphthalenones bearing quaternary stereocenters in good yields with high diastereoselectivities and enantioselectivities.

  通过手性磷酸催化，公开了具有完全原子经济性的 1-取代 2-萘酚和 β,γ-炔基-α-亚氨基酯的高度区域选择性、非对映选择性和对映选择性脱芳构化反应。该协议提供了对广泛的轴向手性丙二烯衍生的萘酮的不对称构建的方便和有效的访问，这些萘酮具有良好的收率，具有高非对映选择性和对映选择性。
• Organocatalytic Enantioselective Synthesis of Tetrasubstituted α‐Amino Allenoates by Dearomative γ‐Addition of 2,3‐Disubstituted Indoles to β,γ‐Alkynyl‐α‐imino Esters
  作者：Junxian Yang、Zheng Wang、Zeyuan He、Guofeng Li、Liang Hong、Wangsheng Sun、Rui Wang

  DOI：10.1002/anie.201911420

  日期：2020.1.7

  phosphoric acid catalyzed dearomative γ-addition reaction of 2,3-disubstituted indoles to β,γ-alkynyl-α-imino esters is reported. This method provides access to a series of highly functionalized tetrasubstituted allenes featuring quaternary stereocenters in high yields, and with excellent regio-, diastereo-, and enantioselectivities under mild conditions without by-product formation. Representative large-scale

  报道了通过2,3-二取代的吲哚手性磷酸催化的β-γ-炔基-α-亚氨基酯的脱芳香族γ-加成反应，首次不对称合成四取代的α-氨基脲酸酯。此方法可提供一系列具有高收率的高官能化四取代的烯，这些化合物具有四级立体中心，并且在温和条件下具有优异的区域，非对映和对映选择性，而不会形成副产物。还公开了代表性的大规模反应和产物向具有潜在生物活性的各种支架的各种转化。通过对照反应和DFT计算阐明了反应机理。
• Oxalylacetylenes as Dielectrophiles for Annulation of Quinoline Rings: Synthesis of Highly Functionalized 1,3-Oxazinoquinolines
  作者：Boris A. Trofimov、Kseniya V. Belyaeva、Lina P. Nikitina、Veronika S. Gen’、Andrei V. Afonin

  DOI：10.1055/a-1644-2930

  日期：2022.4

  quinolines to give highly functionalized 1,3-oxazine cycles decorated with ethynyl, oxalyl, ester and aryl substituents. The annulation proceeds under mild conditions (room temperature, without catalyst) in 2:1 mode with respect to acetylene and quinoline to deliver 1,3-oxazinoquinolines in 45–88% yields. A beneficial feature of the reaction is that, in contrast to results on the reaction of quinolines

  草酰乙炔在喹啉的环化中作为亲电试剂产生高度官能化的 1,3-恶嗪环，该环用乙炔基、草酰基、酯和芳基取代基修饰。环化在乙炔和喹啉的 2:1 模式下在温和条件（室温，无催化剂）下进行，以 45-88% 的产率提供 1,3-恶嗪基喹啉。该反应的一个有益特征是，与喹啉与三氟乙炔在水存在下反应的结果相反，其中 H2O 作为第三个亲电子试剂，导致含有羟基的 1,3-恶嗪基喹啉，该反应很好耐受水性介质。该反应也耐受异喹啉和菲啶。
• A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclo[3.1.0]hexane Frameworks
  作者：Zhen‐Hong Yang、Peng Chen、Zhi‐Chao Chen、Zhi Chen、Wei Du、Ying‐Chun Chen

  DOI：10.1002/anie.202102842

  日期：2021.6.14

  species having an activated alkene moiety through a second deprotonation process, which then undergo cascade [1+2]/[3+2] annulations to furnish complex bicyclic [3.1.0]hexane frameworks having three contiguous quaternary stereogenic centers with good to excellent enantioselectivity. Moreover, by using benzoyl aldehyde-derived substrates, a [1+4]/[3+2] annulation sequence is similarly developed to produce

  在这里，我们报告说，在 Morita-Baylis-Hillman 碳酸盐的存在下，可以实现通过去质子化策略对 Tsuji 的 2-（氰甲基）烯丙基碳酸酯进行化学选择性活化以生成钯-三亚甲基甲烷 1,3-偶极子。以下 S N 2'-加成能够通过第二次去质子化过程形成具有活化烯烃部分的新 1,3-偶极物质，然后进行级联 [1+2]/[3+2] 环化以提供复杂的双环[3.1.0] 己烷骨架具有三个连续的四元立体中心，具有良好到出色的对映选择性。此外，通过使用苯甲醛衍生的底物，类似地开发了 [1+4]/[3+2] 环化序列以产生稠合的环戊二烯 [b] 呋喃结构。