1-(2-methoxyvinyl)-4-(trifluoromethyl)benzene | 1260177-15-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(2-methoxyvinyl)-4-(trifluoromethyl)benzene
• 英文别名: (Z)-1-(2-methoxyvinyl)-4-(trifluoromethyl)benzene；1-(2-methoxyethenyl)-4-(trifluoromethyl)-benzene；(Z)-1-Methoxy-2-[4-(trifluoromethyl)phenyl]ethene；1-[(Z)-2-methoxyethenyl]-4-(trifluoromethyl)benzene
• CAS: 1260177-15-8
• 化学式: C₁₀H₉F₃O
• 分子量: 202.176
• InChiKey: HUQMISIKLCJQFD-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  甲醇 、 4-乙炔基-α,α,α-三氟甲苯 在 二氯二茂钛 、 potassium methanolate 作用下， 以92 %的产率得到1-(2-methoxyvinyl)-4-(trifluoromethyl)benzene
  参考文献：
  名称：

  钛催化炔烃高度立体选择性反马尔可夫尼科夫分子间加氢烷氧基化制备Z-烯醇醚

  摘要：

  烯醇醚是重要的合成骨架，广泛应用于有机合成；然而，高区域和立体选择性获得烯醇醚仍然具有挑战性。在此，我们报道了钛催化的炔烃的立体特异性反马尔可夫尼科夫加氢烷氧基化反应，用于合成具有优异官能团耐受性和产率的Z-烯醇醚。机理研究表明，钛与炔烃配位，然后氧阴离子从背面攻击炔烃的π键，提供反式氧金属化中间体，这解释了高Z立体选择性。此外， Z-烯醇醚可以作为一种合成子用于后期转化和克级合成，这表明了它们在有机合成中的潜在价值。

  DOI：

  10.1039/d3ob01514a

文献信息

• Z-selective, anti-Markovnikov addition of alkoxides to terminal alkynes: an electron transfer pathway?
  作者：James Cuthbertson、Jonathan D. Wilden

  DOI：10.1016/j.tet.2015.04.038

  日期：2015.6

  Potassium alkoxides undergo anti-Markovnikov addition to aryl-substituted alkynes with Z selectivity in DMF as the solvent. The yields and efficiency of the reaction was also found to be enhanced by the addition of a secondary amine ligand such as N,N'-dimethylethylenediamine. Mechanistic investigations suggest that the products, reaction rates and selectivity can be explained via a single electron transfer from the alkoxide to the alkyne. This leads to a radical anion intermediate, which then rapidly combines with the alkoxide to yield a vinyl anion whose lifetime governs the E:Z selectivity observed in the products. (C) 2015 The Authors. Published by Elsevier Ltd.
• Rhodium-Catalyzed Anti-Markovnikov Intermolecular Hydroalkoxylation of Terminal Acetylenes
  作者：Masataka Kondo、Takuya Kochi、Fumitoshi Kakiuchi

  DOI：10.1021/ja1097385

  日期：2011.1.12

  We report here the first transition-metal-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes to give enol ethers in high yields without using bases. Arylacetylenes as well as alkenyl- and alkylacetylenes were coupled with aliphatic alcohols, and the products were obtained with high Z selectivity in most cases. Effective catalysts were 8-quinolinolato rhodium complexes, which are structurally simple but have been relatively unexplored as catalysts.