ethyl 2-oxo-4-(m-tolyl)but-3-enoate | 1375649-22-1

• 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-tolyl)but-3-enoate
• 英文别名: ethyl 2-oxo-4-m-tolyl-3-butenoic ester
• CAS: 1375649-22-1
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: GPCBFAQYLRFMSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-oxo-4-(m-tolyl)but-3-enoate 在 C₃₀H₃₀N₄O₃ 、 silica gel 作用下， 以 对二甲苯 、 甲苯 为溶剂， 反应 13.5h， 生成 (R)-ethyl 5-nitro-2-oxo-4-m-tolylpentanoate
  参考文献：
  名称：

  A practical synthesis of optically active δ-nitro-α-ketoesters and 4-cyclohexyl-proline catalyzed by chiral squamides

  摘要：

  Inexpensive and readily available squamides derived from 9-amino-9-deoxyepiquinine or 9-amino-9-deoxyepiquinidine were found to be superior catalysts for the asymmetric conjugate additions of t-butyl nitroacetate to beta,gamma-unsaturated-alpha-ketoesters. After the subsequent decarboxylation with silica gel, a variety of delta-nitro-alpha-ketoesters were obtained in good yields and with excellent enantioselectivities. The products were further transformed into ethyl 4-aryl-prolinate via a cascade nitro reduction and amination. A new synthesis of (2S,4S)-4-cyclohexyl-proline was also developed. A practical synthesis of optically active delta-nitro-alpha-ketoesters and 4-aryl-proline derivatives is described. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.009

文献信息

• 一种可见光催化[2+2]反应构筑四元环的方法
  申请人：中国科学院理化技术研究所

  公开号：CN108623425B

  公开（公告）日：2021-05-14

  本发明公开一种可见光催化[2+2]反应构筑四元环的方法，包括以下步骤：1.1)将不饱和双键化合物和光敏剂加入溶剂中，得到溶液A；1.2)在氩气环境下，用可见光照射溶液A，得到自身二聚[2+2]环丁烷产物；或2.1)将不饱和双键化合物、苯乙烯类化合物和光敏剂加入溶剂中，得溶液B；2.2)在氩气环境下，用可见光照射溶液B，得到交叉的[2+2]环丁烷产物。本发明首次利用可见光敏化剂，实现非刚性双键的分子间[2+2]环化反应；本发明中光敏剂用量小，反应在氩气环境下利用可见光或者太阳光照射就可以实现，反应条件温和；整个过程简洁，高效，体现了其在有机反应和工业生产中的潜在应用。
• Catalytic Asymmetric Domino Michael/Annulation Reaction of Bifunctional Chromone Synthons with β,γ-Unsaturated α-Keto Esters: Rapid Access to Polysubstituted Spirocyclic Hexahydroxanthones
  作者：Xiong-Li Liu、Ying Zhou、Hao-Jie Zhou、Wei Zhou、You-Ping Tian、Jun-Xin Wang

  DOI：10.1055/s-0040-1707340

  日期：——

  Abstract A thiourea-catalyzed asymmetric domino Michael/annulation process was devised employing bifunctional oxindole-chromones as C4 synthons and β,γ-unsaturated α-keto esters as C2 synthons. This reaction enables the highly diastereo- and enantioselective synthesis of a range of biologically relevant spirocyclic hexahydroxanthones with one quaternary and four tertiary stereogenic centers, also featuring

  摘要 设计了一种硫脲催化的不对称多米诺骨牌迈克尔/环化方法，该方法采用双官能羟吲哚-色酮作为C 4合成子，β，γ-不饱和α-酮酯作为C 2合成子。该反应可实现具有一系列季铵和四级立体异构中心的一系列生物学相关的螺环六氧杂蒽酮的高度非对映体和对映体选择性合成，并具有有趣的两个特权基序的有趣组合，包括六氢黄酮和羟吲哚亚结构，收率高（可达76 ％）和出色的立体选择性（高达> 99％ee和> 20：1 dr）。此外，使用β，γ-不饱和α-酮酯作为C 2不同于烯酮底物（如查尔酮和苯并丙酮）的结构单元，可逆的迈克尔反应进一步扩大了该方法的范围。此外，按比例放大还证明了该协议的适用性。
• 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。
• Highly Enantioselective Friedel-Crafts Reaction of 4,7-Dihydroindoles with β,γ-Unsaturated α-Keto Esters by Chiral Brønsted Acids
  作者：Mi Zeng、Qiang Kang、Qing-Li He、Shu-Li You

  DOI：10.1002/adsc.200800523

  日期：2008.10.6

  A highly efficient Friedel–Crafts reaction of 4,7-dihydroindoles with β,γ-unsaturated α-keto esters by a chiral N-triflyl phosphoramide was realized, affording the 2-substituted 4,7-dihydroindoles with up to 98% ee for a wide range of substrates. The Friedel–Crafts alkylation together with a subsequent oxidation of the product with p-benzoquinone led to a 2-alkylated indole derivative in 98% ee.

  通过手性N-三氟乙磷酰胺实现了4,7-二氢吲哚与β，γ-不饱和α-酮酸酯的高效弗里德-克来福特反应，得到了2-取代的4,7-二氢吲哚，其ee高达98％。多种基材。Friedel-Crafts烷基化反应以及随后用对苯醌氧化产物的反应，在98％ee中生成了2-烷基化的吲哚衍生物。
• Highly Enantioselective and Efficient Organocatalytic Aldol Reaction of Acetone and β,γ-Unsaturated α-Keto Ester
  作者：Pengfei Li、Junling Zhao、Fengbo Li、Albert S. C. Chan、Fuk Yee Kwong

  DOI：10.1021/ol102254q

  日期：2010.12.17

  An effective organocatalytic asymmetric aldol reaction of acetone to β,γ-unsaturated α-keto ester has been developed. In the presence of 5 mol % of 9-amino (9-deoxy)-epicinchona alkaloid and 10 mol % of 4-nitrobenzoic acid, the aldol adducts containing a chiral tertiary alcohol moiety were obtained in excellent yields and enantioselectivities.

  已经开发出一种有效的丙酮与β，γ-不饱和α-酮酯的有机催化不对称醛醇缩合反应。在5mol％的9-氨基（9-脱氧）-表庚酮生物碱和10mol％的4-硝基苯甲酸的存在下，以优异的产率和对映选择性获得了含有手性叔醇部分的羟醛加合物。