ethyl 4-(2,4-dichlorophenyl)-2-oxobut-3-enoate | 1143504-77-1

• 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 4-(2,4-dichlorophenyl)-2-oxobut-3-enoate
• CAS: 1143504-77-1
• 化学式: C₁₂H₁₀Cl₂O₃
• 分子量: 273.116
• InChiKey: MHPXKTGNXMKLQI-UHFFFAOYSA-N

物化性质

• 沸点：
  385.9±42.0 °C(Predicted)
• 密度：
  1.335±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

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：

  别麦芽酚 、 ethyl 4-(2,4-dichlorophenyl)-2-oxobut-3-enoate 在 1-(((1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)-3-(1-(piperidin-1-yl)-2,3-dihydro-1H-inden-2-yl)thiourea 作用下， 以 二氯甲烷 为溶剂， 反应 12.17h， 以92%的产率得到(4R)-ethyl 4-(2,4-dichlorophenyl)-2-hydroxy-6-methyl-8-oxo-2,3,4,8-tetrahydropyrano[3,2-b]pyran-2-carboxylate
  参考文献：
  名称：

  Asymmetric Michael/hemiketalization of 5-hydroxy-2-methyl-4H-pyran-4-one to β,γ-unsaturated α-ketoesters catalyzed by a bifunctional rosin–indane amine thiourea catalyst

  摘要：

  报道了一种使用手性双功能松香-茚胺硫脲催化剂的高效对映选择性Michael-半缩醛化级联过程。

  DOI：

  10.1039/c4ra06938b

文献信息

• Highly stereoselective construction of tetrahydroquinolines via cascade aza-Michael-Michael reaction: Formal [4+2] cycloaddition of β,γ-unsaturated α-ketoesters with 2-aminochalcones
  作者：Cong Duan、Yongqi Yao、Ling Ye、Zhichuan Shi、Zhigang Zhao、Xuefeng Li

  DOI：10.1016/j.tet.2018.10.053

  日期：2018.12

  An efficient cascade aza-Michael-Michael sequence for the preparation of tetrahydroquinolines has been established. Three contiguous stereogenic centers are created with high levels of enantioselectivities (79–99% ee) and exclusive diastereoselectivities in the presence of a bifunctional squaramide. This approach is compatible with a broad range of β,γ-unsaturated α-ketoesters and 2-aminochalcones

  已经建立了用于制备四氢喹啉的有效级联氮杂-迈克尔-迈克尔序列。在双功能方酰胺存在的情况下，创建了三个具有高对映选择性（79-99％ee）和排他性非对映选择性的连续的立体异构中心。该方法与广泛的β，γ-不饱和α-酮酸酯和2-氨基查耳酮相容。我们的协议表明，β，γ-不饱和α-酮酸酯的β-位点是一个可用的亲核位点。
• Highly Enantioselective Organocatalytic Michael Addition of 2-Hydroxy- 1,4-naphthoquinone to β,γ-Unsaturated α-Oxo Esters
  作者：Yi-Feng Wang、Wei Zhang、Shu-Ping Luo、Guang-Cun Zhang、Ai-Bao Xia、Xiang-Sheng Xu、Dan-Qian Xu

  DOI：10.1002/ejoc.201000885

  日期：2010.9

  An organocatalytic enantioselective Michael addition of 2-hydroxy-1,4-naphthoquinone to β,γ-unsaturated α-oxo esters has been developed. The process was promoted by bifunctional chiral amine derived squaramides according to a hydrogen-bonding mediated activation mechanism and afforded the chiral adducts in high yields (up to 88 %) and excellent enantioselectivity (up to 98 % ee) under mild conditions

  已开发出 2-羟基-1,4-萘醌与 β,γ-不饱和 α-氧代酯的有机催化对映选择性迈克尔加成。根据氢键介导的活化机制，双功能手性胺衍生的方酸酰胺促进了该过程，并在温和的条件下以高产率（高达 88%）和优异的对映选择性（高达 98%ee）提供手性加合物。这种有机催化不对称迈克尔加成为合成光学活性官能化萘醌提供了有效途径。
• Chiral Squaramides as Highly Enantioselective Catalysts for Michael Addition Reactions of 4-Hydroxycoumarins and 4-Hydroxypyrone to β,γ-Unsaturated α-Keto Esters
  作者：Dan-Qian Xu、Yi-Feng Wang、Wei Zhang、Shu-Ping Luo、Ai-Guo Zhong、Ai-Bao Xia、Zhen-Yuan Xu

  DOI：10.1002/chem.201000094

  日期：2010.4.12

  Distance brings forth beauty: The first highly enantioselective organocatalytic Michael addition of 4‐hydroxycoumarins and the analogous 4‐hydroxy‐6‐methyl‐2‐pyrone to β,γ‐unsaturated α‐keto esters by using chiral squaramides as the organocatalysts is disclosed. The efficiency of the process is attributed to the hydrogen‐bonding activation (see scheme).

  距离带来美感：公开了通过使用手性方酰胺作为有机催化剂将4-羟基香豆素和类似的4-羟基-6-甲基-2-吡喃酮首次高度对映选择性的迈克尔加成反应，生成β，γ-不饱和α-酮酸酯。该过程的效率归因于氢键活化（参见方案）。
• Enantioselective Asymmetric Michael Addition of Cyclic Diketones to β,γ-Unsaturated α-Keto Esters
  作者：Yi-Feng Wang、Ke Wang、Wei Zhang、Bin-Bin Zhang、Chi-Xiao Zhang、Dan-Qian Xu

  DOI：10.1002/ejoc.201200179

  日期：2012.7

  An efficient, organocatalytic enantioselective addition of cyclic diketones with β,γ-unsaturated α-keto esters has been developed that affords products in high yields (up to 95 %) and excellent enantioselectivity (up to >99 % ee) under mild conditions with a low catalyst loading (2.5 mol-%). The unsaturated α-keto esters are effectively coordinated and activated through hydrogen bonds with the squaramides

  已开发出环状二酮与 β,γ-不饱和 α-酮酯的高效有机催化对映选择性加成，可在温和条件下以高产率（高达 95%）和优异的对映选择性（高达 >99%ee）提供产品低催化剂负载（2.5 mol-%）。不饱和α-酮酯通过与方酸酰胺的氢键有效配位和活化，并被证明是这种不对称有机催化反应中优异的氢键受体。该反应为获得手性迈克尔加合物提供了宝贵且容易的途径，这是生物和药物分子骨架中的重要部分。
• Organocatalyzed Asymmetric Michael Addition of 1-Acetylindolin-3-ones to β,γ-Unsaturated α-Ketoesters: An Access to Chiral Indolin-3-ones with Two Adjacent Tertiary Stereogenic Centers
  作者：Shanren Chen、Youming Wang、Zhenghong Zhou

  DOI：10.1021/acs.joc.6b02070

  日期：2016.11.18

  Asymmetric Michael addition of 1-acetylindolin-3-ones to β,γ-unsaturated α-ketoesters was investigated for the synthesis of chiral indolin-3-ones with two adjacent tertiary stereogenic centers. Under the catalysis of a chiral bifunctional squaramide derived from l-tert-leucine, a wide range of 1-acetylindolin-3-ones and β,γ-unsaturated α-ketoesters were well-tolerated in this transformation to provide

  研究了1-乙酰基吲哚-3-酮向β，γ-不饱和α-酮酸酯的不对称Michael加成反应，用于合成具有两个相邻的叔立体中心的手性吲哚-3-酮。下的催化手性双官能squaramide衍生自升-叔-亮氨酸，范围广泛的1- acetylindolin -3-酮和β，γ不饱和α酮酯是在这一转变，以提供相应的新颖密集官能良好耐受在温和的反应条件下，高收率的手性吲哚-3-酮衍生物，具有出色的非对映选择性和对映选择性。