ethyl 2-oxo-4-(m-bromophenyl)but-3-enoate | 1375649-12-9

• 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: ethyl 2-oxo-4-(m-bromophenyl)but-3-enoate
• 英文别名: Ethyl 4-(3-bromophenyl)-2-oxobut-3-enoate
• CAS: 1375649-12-9
• 化学式: C₁₂H₁₁BrO₃
• 分子量: 283.122
• InChiKey: XZWRTWNTPLDTEM-UHFFFAOYSA-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：

  ethyl 2-oxo-4-(m-bromophenyl)but-3-enoate 在 palladium on activated charcoal 、 (S)-N-(1-hexadecyl-1H-imidazol-2-yl)pyrrolidine-2-carboxamide 、 氢气 、 丙酸 作用下， 以 乙腈 为溶剂， 生成 (2R,3R)-ethyl 2-(3-bromophenethyl)-2,3-dihydroxy-4-oxopentanoate
  参考文献：
  名称：

  Construction of anti-1,2-diols bearing chiral tertiary alcohol moiety using free hydroxyacetone as aldol donor by imidazole-based prolineamide catalyst

  摘要：

  A direct aldol reaction of free hydroxyacetone and activated ketone has been firstly achieved with a newly developed imidazole-based prolineamide catalyst. The adducts anti-1,2-diols bearing a chiral tertiary alcohol moiety were obtained in high yield (up to 92%) and stereoselectivity (up to 15:1 dr and 90% ee). (C) 2014 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2014.07.015
• 作为产物：
  描述：

  间溴苯甲醛 在 乙酰氯 、 potassium hydroxide 作用下， 以 甲醇 为溶剂， 反应 21.0h， 生成 ethyl 2-oxo-4-(m-bromophenyl)but-3-enoate
  参考文献：
  名称：

  三甲基铝的对映选择性铜催化共轭加成反应，生成β，γ-不饱和α-酮酸酯

  摘要：

  尚未解决：将有机金属试剂铜催化的不对称共轭加成至Michael受体是一种以对映选择性的方式形成C bondC键的重要方法。据描述，向β，γ-不饱和α-酮酸酯中添加Me 3 Al可以提高收率和选择性。CuTC =噻吩-2-羧酸铜（I）。

  DOI：

  10.1002/anie.201107324

文献信息

• Highly diastereoselective synthesis of trifluoromethyl containing spiro[pyrrolidin-3,2′-oxindoles] from N-2,2,2-trifluoroethylsubstituted isatin imines and β,γ-unsaturated α-keto esters
  作者：Ya Xiong、Xiao-Xue Han、Yu Lu、Hui-Juan Wang、Min Zhang、Xiong-Wei Liu

  DOI：10.1016/j.tet.2021.132112

  日期：2021.5

  Inspired by the chemistry and biology of fluorine-containing molecules and pyrrolidinyl spirooxindoles, herein we report a highly diastereoselective [3 + 2] cycloaddition reaction of β,γ-unsaturated α-keto esters and N-2,2,2-trifluoroethylisatin ketimines in the presence of the catalyst DABCO. The process enables efficient incorporation of CF3 groups into pharmaceutically important spiro[pyrrolidin-3

  受含氟分子和吡咯烷基螺氧辛酯的化学和生物学影响，本文报道了β，γ-不饱和α-酮酯和N-2,2,2-三氟乙基异丁烯酮酮的非对映选择性[3 + 2]环加成反应。催化剂DABCO的存在。该方法能够将CF 3基团有效地掺入药学上重要的螺[吡咯烷烃3,2'-羟吲哚]，并具有四个连续的立体异构中心，包括一个四取代碳，效率高（产率高达93％，非对映异构体> 20：1）比率）。此外，使用β，γ-不饱和α与该烯酮底物（如查尔酮和苯并丙酮）不同的是，在此反应中作为2C结构单元的-酮酸酯进一步扩大了它们的适用范围。
• Chiral Bifunctional Squaramide-Catalyzed Highly Enantioselective Michael Addition of Allomaltol to β,γ-Unsaturated α-Ketoesters
  作者：Yunting Liu、Qiaohui Wang、Youming Wang、Haibin Song、Zhenghong Zhou

  DOI：10.1002/cctc.201402168

  日期：2014.8

  A highly enantioselective Michael addition of allomaltol (5‐hydroxy‐2‐methyl‐4H‐pyran‐4‐one) to both aromatic and aliphatic β,γ‐unsaturated α‐ketoesters has been realized. Under the catalysis of a chiral bifunctional tertiary amine‐squaramide that bears a (1R,2R)‐1,2‐diphenylethane‐1,2‐diamine scaffold, the reaction proceeded smoothly with high levels of enantioselectivity to give the desired products

  已实现对芳香族和脂肪族β，γ-不饱和α-酮酸酯都具有高度对映体选择性的麦芽酚（5-羟基-2-甲基-4-甲基4 H-吡喃-4-酮）的迈克尔加成反应。在带有（1 R，2 R）-1,2-二苯乙烷-1,2-二胺骨架的手性双官能叔胺-方胺的催化下，反应进行得很顺利，对映选择性很高，从而可以得到所需的产物。可接受的收率，对映体过量86-> 99％。该方法为旋光活性曲酸衍生物的对映选择性合成提供了一种有效的方法。
• Construction of 9<i>H</i>-Pyrrolo[1,2-<i>a</i>]indoles by a Copper-Catalyzed Friedel–Crafts Alkylation/Annulation Cascade Reaction
  作者：Yongqing Sun、Yu Qiao、Haiying Zhao、Baoguo Li、Shufeng Chen

  DOI：10.1021/acs.joc.6b02143

  日期：2016.12.2

  Cu(OTf)2-catalyzed Friedel–Crafts alkylation/annulation cascade reaction of substituted indoles with 1,2-dicarbonyl-3-enes has been established. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of diverse 9H-pyrrolo[1,2-a]indoles bearing a carbonyl group.

  建立了高效，简明的Cu（OTf）2催化的取代吲哚与1,2-二羰基-3-烯的吲哚的Friedel-Crafts烷基化/环化级联反应。该反应使用容易获得的起始原料并且操作简单，因此代表了用于构建带有羰基的多种9 H-吡咯并[1,2- a ]吲哚的实用方法。
• The Vinylogous Michael Addition of 3‐Alkylidene‐2‐oxindoles to β,γ‐Unsaturated α‐Keto Esters by Bifunctional Cinchona Alkaloids
  作者：Manish K. Jaiswal、Rajesh Kumar、Sanjay Singh、Shailija Jain、Kumar Vanka、Ravi P. Singh

  DOI：10.1002/ejoc.202000835

  日期：2020.9.22

  A highly enantioselective vinylogous Michael addition of 3‐alkylidene‐2‐oxindoles with β,γ‐unsaturated α‐keto esters using a bifunctional tertiary‐amine thiourea catalyst is demonstrated. The challenging Michael reaction with the β,γ‐unsaturated α‐keto esters has been accomplished due to the synchronized H‐bond guided dual activation of vinylogous nucleophile and electrophile by catalyst. The reaction

  证明了使用双官能叔胺硫脲催化剂，对3-亚烷基-2-氧吲哚和β，γ-不饱和α-酮酯的高对映选择性乙烯基迈克尔加成反应。由于催化剂通过同步的H键引导对乙烯基亲核试剂和亲电试剂的双重活化，已经完成了与β，γ-不饱和α-酮酸酯的具有挑战性的迈克尔反应。该反应以高收率提供产物，同时导致优异的立体控制（高达99％ee和> 19：1 E / Z）。
• Organocatalytic asymmetric Michael-type reaction between β,γ-unsaturated α-keto ester and α-nitro ketone
  作者：Pengfei Li、Sau Hing Chan、Albert S. C. Chan、Fuk Yee Kwong

  DOI：10.1039/c1ob06191g

  日期：——

  A Michael-type reaction of β,γ-unsaturated α-keto ester and α-nitro ketone was established. With a thiourea catalyst derived from cinchona alkaloid, the reactions afford products in 47–94% yields with 68–96% ee.

  建立了β，γ-不饱和α-酮酯与α-硝基酮的迈克尔型反应。用金鸡纳生物碱衍生的硫脲催化剂，反应可提供47-94％收率和68-96％ee的产物。