methyl 2,2-bis(trifluoromethyl)pent-4-enoate | 18448-21-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 2,2-bis(trifluoromethyl)pent-4-enoate
• 英文别名: 2,2-Bis-(trifluormethyl)-5,5-difluor-penten-(4)-saeuremethylester；2,2-Di(trifluoromethyl)-4-pentenoic acid methyl ester
• CAS: 18448-21-0
• 化学式: C₈H₈F₆O₂
• 分子量: 250.141
• InChiKey: NQXVZNRKBVIHBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  烯丙基甲基碳酸酯 、 2-(三氟甲基)-3,3,3-三幅丙酸甲酯 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以35%的产率得到methyl 2,2-bis(trifluoromethyl)pent-4-enoate
  参考文献：
  名称：

  Pd-Catalyzed Allylic Alkylation of CF3-Containing Esters with Three Electron-Withdrawing Groups

  摘要：

  Tsuji-Trost reaction (Pd-catalyzed allylic alkylation) of CF3-containing esters with three electron-withdrawing groups is reported. The reactions with methyl bis(trifluoromethyl) acetate and dimethyl ( trifluoromethyl) malonate were carried out with low-loading catalysts of Pd(0) and XPhos at ambient temperature in THF, giving the products in high yields. This method efficiently overcomes the beta-defluorination, which is hard to control in the chemical transformation of alpha-trifluoromethyl carbanions, and provides versatile fluorinated compounds with quaternary carbon centers, which are highly demanded in drug discovery.

  DOI：

  10.1055/s-0032-1318313

文献信息

• Negative substituents in the claisen rearrangement
  作者：C.G. Krespan

  DOI：10.1016/s0040-4020(01)88821-9

  日期：1967.1

  instances of the Claisen rearrangement are demonstrated with allyl vinyl ethers in which the vinyl segment is heavily substituted with negative groups. With fluoro, fluoroalkyl, chloro and alkoxy as negative substituents, these reactions proceed with unusual ease at 25–100°. A related isomerization of a propargyl vinyl ether to an allenyl ketone is also described.

  用烯丙基乙烯基醚证明了克莱森重排的几种情况，其中乙烯基链段被负基团严重取代。用氟，氟烷基，氯和烷氧基作为负取代基，这些反应在25–100°的温度下异常容易地进行。还描述了炔丙基乙烯基醚到烯丙基酮的相关异构化。
• US7511179B2
  申请人：——

  公开号：US7511179B2

  公开（公告）日：2009-03-31
• Pd-Catalyzed Allylic Alkylation of CF3-Containing Esters with Three Electron-Withdrawing Groups
  作者：Yong Guo、Lun Li、Donghui Huang、Qing-Yun Chen

  DOI：10.1055/s-0032-1318313

  日期：——

  Tsuji-Trost reaction (Pd-catalyzed allylic alkylation) of CF3-containing esters with three electron-withdrawing groups is reported. The reactions with methyl bis(trifluoromethyl) acetate and dimethyl ( trifluoromethyl) malonate were carried out with low-loading catalysts of Pd(0) and XPhos at ambient temperature in THF, giving the products in high yields. This method efficiently overcomes the beta-defluorination, which is hard to control in the chemical transformation of alpha-trifluoromethyl carbanions, and provides versatile fluorinated compounds with quaternary carbon centers, which are highly demanded in drug discovery.