ethyl (1R,5S)-2-oxo-3,4-diphenyl-5-[4-(trifluoromethyl)phenyl]cyclopent-3-ene-1-carboxylate | 1236274-48-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: ethyl (1R,5S)-2-oxo-3,4-diphenyl-5-[4-(trifluoromethyl)phenyl]cyclopent-3-ene-1-carboxylate
• CAS: 1236274-48-8
• 化学式: C₂₇H₂₁F₃O₃
• 分子量: 450.457
• InChiKey: WPQNELIMKXPWCZ-LADGPHEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  ethyl 3-oxo-4,5-diphenyl-2-[[4-(trifluoromethyl)phenyl]methylidene]pent-4-enoate 在 iron(II) triflate 、 2,6-二[(4S)-4-叔丁基-2-恶唑啉基]吡啶 作用下， 以 甲苯 为溶剂， 以89%的产率得到ethyl (1R,5S)-2-oxo-3,4-diphenyl-5-[4-(trifluoromethyl)phenyl]cyclopent-3-ene-1-carboxylate
  参考文献：
  名称：

  Iron- or Cobalt-Catalyzed Nazarov Cyclization: Asymmetric Reaction and Tandem Cyclization-Fluorination Reaction

  摘要：

  我们成功地证明了铁或钴催化的二乙烯酮不对称纳扎罗夫环化反应，这些催化剂是由Co(ClO4)2Ë6H2O、Fe(ClO4)2Ë6H2O或Fe(OTf)2与手性吡咯类配体制备而成的。此外，我们还发现，Fe(OTf)2 能有效催化二乙烯酮的串联纳扎罗夫环化-氟化反应。

  DOI：

  10.1055/s-0029-1219782

文献信息

• Development of Solvent-Driven Iron-Catalyzed Reactions
  作者：Toshiyuki Itoh

  DOI：10.3987/rev-16-842

  日期：——

  The possibility of solvent-driven iron-catalyzed reactions has been investigated using ionic liquids and acetonitrile as key solvents. Three iron-catalyzed reactions, the intramolecular cyclization of cyclopropane dithioacetals, the [2+2]-cycloaddition of (trans)-anethole, and the [2+3]-type cycloaddition of styrene derivatives with 1,4-benzoquinone, were first developed using acetonitrile as solvent in the presence of 3 similar to 5 mol% of Fe(ClO4)(3)center dot Al2O3 or Fe(BF4)(2)center dot 6H(2)O under air conditions. In particular, we found the rapid cycloaddition of iron-catalyzed [2+3]-type cycloaddition of styrene derivatives with 1,4-benzoquinone when the reaction was carried out in an ionic liquid which contained [PF6] or [Tf2N] anion. Homo-coupling reaction of aryl or alkynyl Grignard reagent was next discovered using 1 mol% of FeCl3 as catalyst and the reaction also proceeded very rapidly in an ionic liquid. We also found that 3-5 mol% of Fe(ClO4)(2)center dot Al2O3 or Fe(BF4)(2)center dot 6H(2)O-successfully catalyzed Friedel-Crafts type alkylation of indoles or pyrroles with vinyl ketones or alpha-aryl-beta-silylalcohol. In particular, the reaction of chiral alpha-aryl-beta-silylalcohol with indole using Fe(ClO4)(3)center dot nH(2)O as catalyst proceeded with retention of the configuration of stereochemistry of the hydroxyl group. Then, we discovered the first example of iron-catalyzed enantioselective C-S bond formation via Michael addition of thiols to (E)-3-crotonoyloxazolidin-2-one using 10 mol% of Fe(BF4)(2)/Pybox. We further demonstrated that Fe(ClO4)(3)center dot Al2O3-catalyzed the Nazarov type cyclizations of thiophene, pyrrole, indole, benzofuran, and benzo[b]thiophene derivatives using ionic liquids as solvent. Solvents have been recognized as a by-player in chemical reactions in the process of "optimization of reaction conditions". However, further investigation of the solvent-driven iron-catalyzed reaction will allow discovery of useful reactions for organic syntheses.