ethyl phenylsulfonyl(4-trifluoromethylphenyl)acetate

• 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: ethyl phenylsulfonyl(4-trifluoromethylphenyl)acetate
• 英文别名: ethyl(p-trifluoromethylphenyl)phenylsulfonylacetate；Benzenesulfonyl(4-trifluoromethylphenyl)acetic acid, ethyl ester；ethyl 2-(benzenesulfonyl)-2-[4-(trifluoromethyl)phenyl]acetate
• 化学式: C₁₇H₁₅F₃O₄S
• 分子量: 372.365
• InChiKey: JYPYBYPOXVSJBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  对溴三氟甲苯 、 苯砜乙酸乙酯 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 1,1'-双(二苯基膦)二茂铁 、 sodium hydride 作用下， 以 1,4-二氧六环 为溶剂， 反应 4.0h， 以77%的产率得到ethyl phenylsulfonyl(4-trifluoromethylphenyl)acetate
  参考文献：
  名称：

  碱在钯催化的碳负离子芳基化中的作用

  摘要：

  某些砜，氰基乙酸酯和丙二腈衍生的碳负离子与芳基溴化物的芳基化反应（使用Pd 2 dba 3 / 3L的催化体系，L = PPh 3，P t Bu 3）以及碳负离子的反应一当量的4-CF 3 C 6 H 4 Pd（PPh 3）2溴已被研究。只要反应混合物中存在比初始碳负离子强的碱，这些反应就可以顺利进行。在没有上述类型的碱的情况下，反应根本不进行。考虑到这一点，我们提出了钯催化CH-酸芳基化的新机制。该机理的主要特征是由于中间ArPdL 2 CHXY的去质子化而加速了还原消除。在所提出的机理的框架内，讨论了碳负离子反应性和相关CH-酸的p K a值之间的相关性以及配体效应。

  DOI：

  10.1016/j.jorganchem.2003.12.039

文献信息

• Role of base in palladium-catalyzed arylation of carbanions
  作者：Anton V Mitin、Alexander N Kashin、Irina P Beletskaya

  DOI：10.1016/j.jorganchem.2003.12.039

  日期：2004.3

  proposed a novel mechanism of palladium-catalyzed arylation of CH-acids. The main feature of this mechanism is the accelaration of the reductive elimination due to the deprotonation of the intermediate ArPdL2CHXY. The correlation between the carbanion reactivity and the pKa values for related CH-acids as well as the ligand effect are discussed in the framework of the proposed mechanism.

  某些砜，氰基乙酸酯和丙二腈衍生的碳负离子与芳基溴化物的芳基化反应（使用Pd 2 dba 3 / 3L的催化体系，L = PPh 3，P t Bu 3）以及碳负离子的反应一当量的4-CF 3 C 6 H 4 Pd（PPh 3）2溴已被研究。只要反应混合物中存在比初始碳负离子强的碱，这些反应就可以顺利进行。在没有上述类型的碱的情况下，反应根本不进行。考虑到这一点，我们提出了钯催化CH-酸芳基化的新机制。该机理的主要特征是由于中间ArPdL 2 CHXY的去质子化而加速了还原消除。在所提出的机理的框架内，讨论了碳负离子反应性和相关CH-酸的p K a值之间的相关性以及配体效应。
• Palladium-catalyzed arylation of sulfonyl CH-acids
  作者：Alexander N Kashin、Anton V Mitin、Irina P Beletskaya、Richard Wife

  DOI：10.1016/s0040-4039(02)00321-0

  日期：2002.4

  A method for the palladium-catalyzed monoarylation of a series of functionalized sulfones by aryl halides is described. The reaction proceeds in the presence of 2 mol%, of Pd(2)dba(3)(.)CHCl(3) (dba=dibenzylideneacetone), PPh3 and NaH as a base, only with relatively strong CH-acids and gives monoarylated products in moderate to high yields. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Palladium-Catalyzed Arylation of Sulfones
  作者：A. V. Mitin、A. N. Kashin、I. P. Beletskaya

  DOI：10.1023/b:rujo.0000044542.70121.04

  日期：2004.6

  A procedure was developed for monoarylation of sulfones with aryl halides in the presence of palladium complexes. Optimal reaction conditions were found, and the scope of application of the proposed procedure was determined. The arylation occurs only with those sulfones which are relatively strong CH acids, the corresponding monoarylated sulfones are formed in moderate to high yields. The arylation of carbanions derived from the sulfones and some other CH acids requires the presence of an additional equivalent of base. The presence of the latter is also necessary in stoichiometric reactions of carbanions with the palladium complex CF3C6H4Pd(PPh3)(2)Br; no reaction occurs in the absence of a base. A new mechanism of arylation was proposed, where the key stage is deprotonation of palladium intermediate ArPdL2CHXY which activates the reductive elimination stage.