(E)-ethyl 4-(2-chlorophenyl)-2-oxobut-3-enoate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-ethyl 4-(2-chlorophenyl)-2-oxobut-3-enoate
• 英文别名: ethyl (E)-4-(2-chlorophenyl)-2-oxobut-3-enoate
• 化学式: C₁₂H₁₁ClO₃
• 分子量: 238.671
• InChiKey: PBUSDFVMNBMONV-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  5
• 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：

  (E)-ethyl 4-(2-chlorophenyl)-2-oxobut-3-enoate 、 三乙基硅烷 在 indium(III) chloride 、 三氟乙酸 作用下， 以 甲苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 0.5h， 以57%的产率得到(Z)-ethyl 4-(2-chlorophenyl)-2-((triethylsilyl)oxy)but-2-enoate
  参考文献：
  名称：

  A Mild Method for Indium(III)-Catalyzed 1,4-Hydrosilylation of α,β-Enone Esters with Triethylsilane and Trifluoroacetic Acid

  摘要：

  A chemo- and stereoselective 1,4-hydrosilylation of alpha,beta-enone esters was developed using triethylsilane and trifluoroacetic acid under indium chloride catalysis.

  DOI：

  10.1055/s-0031-1290448
• 作为产物：
  描述：

  2-氯苯甲醛 在 乙酰氯 、 potassium hydroxide 作用下， 以 甲醇 为溶剂， 反应 8.0h， 生成 (E)-ethyl 4-(2-chlorophenyl)-2-oxobut-3-enoate
  参考文献：
  名称：

  A Mild Method for Indium(III)-Catalyzed 1,4-Hydrosilylation of α,β-Enone Esters with Triethylsilane and Trifluoroacetic Acid

  摘要：

  A chemo- and stereoselective 1,4-hydrosilylation of alpha,beta-enone esters was developed using triethylsilane and trifluoroacetic acid under indium chloride catalysis.

  DOI：

  10.1055/s-0031-1290448

文献信息

• Direct Synthesis of β,γ-Unsaturated α-Keto Esters from Aldehydes and Pyruvates
  作者：John Mansaray、Jiarui Sun、Shisheng Huang、Weijun Yao

  DOI：10.1055/s-0037-1612255

  日期：2019.4

  methods to synthesize β,γ-unsaturated α-keto esters directly from aldehydes and pyruvates promoted by BF3•Et2O in the presence of Ac2O or by Ti(OEt)4 under mild conditions. A variety of aromatic aldehydes was tolerated to afford the desired products in moderate to excellent yield. Moreover, aliphatic aldehydes and Isatin were also employed to give the γ-alkyl β,γ-unsaturated α-keto esters in moderate yield

  在这里，我们描述了两种实用的方法，在温和条件下，在 Ac2O 或 Ti(OEt)4 存在下，由 BF3•Et2O 促进的醛和丙酮酸盐直接合成 β,γ-不饱和 α-酮酯。可以耐受各种芳香醛，以中等至极好的收率提供所需的产品。此外，脂肪醛和靛红也被用于通过使用 Ti(OEt)4 系统以中等产率得到 γ-烷基 β,γ-不饱和 α-酮酯。
• Copper-Catalyzed Chemoselective and Enantioselective Friedel–Crafts 1,2-Addition of Pyrrole with β,γ-Unsaturated α-Ketoesters
  作者：Jianan Sun、Yanbin Hu、Yanan Li、Sheng Zhang、Zhenggen Zha、Zhiyong Wang

  DOI：10.1021/acs.joc.7b00159

  日期：2017.5.19

  A Friedel–Crafts alkylation of pyrrole was developed to afford the β,γ-unsaturated α-hydroxy esters bearing a quaternary stereogenic center with good enantioselectivities and yields. This protocol represents the first report of 1,2-addition of Friedel–Crafts alkylation of pyrrole to β,γ-unsaturated α-ketoesters.

  开发了吡咯的弗瑞德-克拉夫茨烷基化反应，以提供带有良好立体异构性和收率的季立体中心的β，γ-不饱和α-羟基酯。该方案代表了有关吡咯的Friedel-Crafts烷基化反应成β，γ-不饱和α-酮酸酯的第一个报告。
• Copper Catalyzed Enantioselective Alkylation of Pyrrole with β,γ-Unsaturated α-Ketoesters: Application to One-Pot Construction of the Seven-Membered Ring by Merging a Gold Catalysis
  作者：Yanbin Hu、Yanan Li、Sheng Zhang、Chong Li、Lijun Li、Zhenggen Zha、Zhiyong Wang

  DOI：10.1021/acs.orglett.5b01917

  日期：2015.8.21

  A highly enantioselective Friedel Crafts alkylation of pyrrole to beta,gamma-unsaturated alpha-ketoesters was developed by virtue of a chiral copper complex, affording the alkylated derivatives of pyrrole with good yields and excellent enantioselectivities. Moreover, merging copper catalysis with gold catalysis realized a one-pot construction of the seven-membered ring to give annulated pyrroles with moderate to good yields and high enantiomeric excesses.
• Deracemisation of aryl substituted α-hydroxy esters using Candida parapsilosis ATCC 7330: effect of substrate structure and mechanism
  作者：B. Baskar、N.G. Pandian、K. Priya、Anju Chadha

  DOI：10.1016/j.tet.2005.09.104

  日期：2005.12

  Candida parapsilosis ATCC 7330 was found to be an efficient biocatalyst for the deracemisation of aryl alpha-hydroxy esters (65-85% yield and 90-99% ee). A variety of aryl and aryl substituted alpha-hydroxy esters were synthesized to reflect steric and electronic effects on biocatalytic deracemisation. The mechanism of this biocatalytic deracemisation was found to be stereoinversion. (c) 2005 Elsevier Ltd. All rights reserved.
• A Mild Method for Indium(III)-Catalyzed 1,4-Hydrosilylation of α,β-Enone Esters with Triethylsilane and Trifluoroacetic Acid
  作者：Biao Jiang、Ping Xing、Wei Zang、Zuo-gang Huang、Yue-xiong Zhan、Chuan-jun Zhu

  DOI：10.1055/s-0031-1290448

  日期：——

  A chemo- and stereoselective 1,4-hydrosilylation of alpha,beta-enone esters was developed using triethylsilane and trifluoroacetic acid under indium chloride catalysis.