(E)-ethyl 4-(2-bromophenyl)-2-oxobut-3-enoate | 1257874-32-0

• 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-bromophenyl)-2-oxobut-3-enoate
• 英文别名: ethyl (E)-4-(2-bromophenyl)-2-oxobut-3-enoate
• CAS: 1257874-32-0
• 化学式: C₁₂H₁₁BrO₃
• 分子量: 283.122
• InChiKey: NPDGYSCDQMZWRU-BQYQJAHWSA-N

物化性质

• 沸点：
  368.4±34.0 °C(predicted)
• 密度：
  1.439±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

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：

  吡咯 、 (E)-ethyl 4-(2-bromophenyl)-2-oxobut-3-enoate 在 (S)-2-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-6-(trifluoromethyl)phenol 、 copper(II) bis(trifluoromethanesulfonate) 、 三乙胺 作用下， 以 异丙醇 为溶剂， 反应 1.5h， 以85%的产率得到ethyl (S)-4-(2-bromophenyl)-2-oxo-4-(1H-pyrrol-2-yl)butanoate
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/acs.orglett.5b01917
• 作为产物：
  描述：

  邻溴苯甲醛 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-bromophenyl)-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。
• DABCO-catalyzed regioselective cyclization reactions of β,γ-unsaturated α-ketophosphonates or β,γ-unsaturated α-ketoesters with allenic esters
  作者：Cheng-Kui Pei、Lei Wu、Zhong Lian、Min Shi

  DOI：10.1039/c1ob06507f

  日期：——

  Highly efficient DABCO-catalyzed [4 + 2] cycloaddition of β,γ-unsaturated α-ketophosphonates or β,γ-unsaturated α-ketoesters with allenic esters gives the corresponding highly functionalized tetrahydropyran and dihydropyran derivatives in good to excellent yields and moderate to good regioselectivities under mild conditions.

  高效的DABCO催化的[4 + 2]与烯丙酸酯的β，γ-不饱和α-酮膦酸酯或β，γ-不饱和α-酮酸酯的环加成反应得到相应的高度官能化 四氢吡喃 和二氢吡喃衍生物，在温和条件下具有良好至优异的收率和中等至良好的区域选择性。
• 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.
• 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.