ethyl 4-(3,4-dichlorophenyl)-2-oxobut-3-enoate | 1210054-88-8

• 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 4-(3,4-dichlorophenyl)-2-oxobut-3-enoate
• CAS: 1210054-88-8
• 化学式: C₁₂H₁₀Cl₂O₃
• 分子量: 273.116
• InChiKey: AVMBCIHLUQOQIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  4-methyl-hexa-4,5-dien-3-one 、 ethyl 4-(3,4-dichlorophenyl)-2-oxobut-3-enoate 在 C₅₁H₆₁F₆N₂O₄PSi₂ 作用下， 以 乙醚 为溶剂， 反应 48.0h， 以92%的产率得到ethyl (4S,2Z)-4-(3,4-dichlorophenyl)-2-(3-oxopentan-2-ylidene)-3,4-dihydro-2H-pyran-6-carboxylate
  参考文献：
  名称：

  通过膦催化的 [4+2] 联苯酮和 β,γ-不饱和 α-酮酯的环化反应高度对映选择性合成 3,4-二氢吡喃

  摘要：

  设计了一种膦催化的新型 [4+2] 环化过程，使用丙二烯酮作为 C2 合成子和 β,γ-不饱和 α-酮酯作为 C4 合成子。在 L-苏氨酸衍生的双功能膦存在下，以高产率和几乎完美的对映选择性获得 3,4-二氢吡喃。二氢吡喃基序的合成价值通过抗高胆固醇血症剂的简洁制备得到证明。

  DOI：

  10.1021/ja5109358

文献信息

• Asymmetric Binary-Acid Catalysis with InBr3 in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of Mono- and Bis-Substituted Cyclopentadienes: Remote Fluoro-Effect on Stereocontrol
  作者：Jian Lv、Long Zhang、Shenshen Hu、Jin-Pei Cheng、Sanzhong Luo

  DOI：10.1002/chem.201103340

  日期：2012.1.16

  Remote F effect: Unprecedented hetero‐Diels–Alder reactions of mono‐ and bis‐substituted cyclopentadienes have been realized by an asymmetric binary‐acid catalyst that synergistically combines a chiral phosphoric acid 1 h/InBr3 with good periselectivity, high regioselectivity, and excellent stereoselectivity. Substituent mapping of the chiral phosphoric acid indicates a dramatic remote ortho‐fluoro

  遥远的F效应：单和双取代的环戊二烯的前所未有的杂狄尔斯-阿尔德反应已通过不对称的二元酸催化剂实现，该催化剂将手性磷酸1 h / InBr 3协同结合，具有良好的选择性，高区域选择性和优异的选择性立体选择性。手性磷酸的取代基作图表明对立体控制有显着的远距离邻氟影响（参见方案）。
• Divergent Coupling of β,γ-Unsaturated α-Ketoesters with Simple Olefins: Vinylation and [2 + 2] Cycloaddition
  作者：Le Wang、Jian Lv、Sujia Li、Sanzhong Luo

  DOI：10.1021/acs.orglett.7b01291

  日期：2017.7.7

  Catalytic direct conjugate addition and [2 + 2] cycloaddition reactions of β,γ-unsaturated α-ketoesters with simple olefins have been developed, affording vinylation products and functionalized cyclobutanes, respectively, in good yields with high regioselectivity.

  已经开发出β，γ-不饱和α-酮酸酯与简单烯烃的催化直接共轭加成和[2 + 2]环加成反应，分别以良好的产率和高的区域选择性提供乙烯基化产物和官能化的环丁烷。
• Asymmetric Binary-Acid Catalysis with Chiral Phosphoric Acid and MgF₂: Catalytic Enantioselective Friedel−Crafts Reactions of β,γ-Unsaturated α-Ketoesters
  作者：Jian Lv、Xin Li、Long Zhong、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1021/ol1000928

  日期：2010.3.5

  A unique binary chiral phosphoric acid 1a/MgF2 catalyst that enables effective catalysis of asymmetric Friedel−Crafts reactions of phenols with up to 82% yield and >99% ee is presented. A dramatic synergistic effect has been observed in the combinations of two types of acids, wherein a highly active binary-acid catalyst can be generated from two individually inert acids.

  介绍了一种独特的二元手性磷酸1a / MgF 2催化剂，该催化剂能够以高达82％的收率和> 99％ee的效率有效催化酚的不对称Friedel-Crafts反应。在两种类型的酸的组合中已经观察到显着的协同作用，其中可以由两种单独的惰性酸产生高活性的二元酸催化剂。
• Switchable Enantioselectivity in Conjugate Alkyne Addition of β,γ-Unsaturated α-Keto Esters by Asymmetric Binary Acid Catalysis
  作者：Depeng Duan、Mengdie Tang、Man Wang、Huixin Qiu、Ran Song、Daoshan Yang、Jian Lv

  DOI：10.1021/acs.orglett.4c01101

  日期：2024.5.3

  Switchable enantioselectivity was uncovered in the enantioselective catalytic conjugate addition of β,γ-unsaturated α-keto esters with terminal alkynes to the chiral Lewis acid complex of In(BF4)3 and chiral phosphoric acid.

  在将带有末端炔烃的 β,γ-不饱和 α-酮酯与 In(BF 4 ) 3和手性磷酸的手性路易斯酸络合物进行对映选择性催化共轭加成时，发现了可切换的对映选择性。
• H8-BINOL chiral imidodiphosphoric acids catalyzed cyclization reactions of β,γ-unsaturated α-ketoesters, arylamines and 1,3-dicarbonyl compounds: enantioselective synthesis of 1,4-dihydropyridines
  作者：Dong An、Ziqian Zhu、Guangliang Zhang、Yang Gao、Jigang Gao、Xu Han、Liangyu Zheng、Suoqin Zhang

  DOI：10.1016/j.tetasy.2015.06.019

  日期：2015.9

  Penta-substituted 1,4-dihydropyridines were synthesized via catalytic enantioselective cyclization reactions of beta,gamma-unsaturated alpha-ketoesters, arylamines and acetylacetone for the first time. H-8-BINOL-type chiral imidodiphosphoric acid 4c was a suitable catalyst and exhibited high catalytic and stereocontrolling abilities in these enone-type reactions. Under the optimized conditions, these 1,4-dihydropyridines were obtained with excellent enantioselectivities (up to 97% ee). In addition, the typical product 8ba was converted into the corresponding substituted piperidine with high yield (87%) and excellent enantioselectivity (95% ee) in a single-step reduction. (C) 2015 Elsevier Ltd. All rights reserved.