Lin Jin-Shun, Liu Xiang-Geng, Zhu Xiao-Long, Tan Bin, Liu Xin-Yuan
Department of Chemistry, South University of Science and Technology of China , Shenzhen 518055, People's Republic of China.
J Org Chem. 2014 Aug 1;79(15):7084-92. doi: 10.1021/jo5012619. Epub 2014 Jul 16.
The first example of a copper(I)-catalyzed intramolecular aminotrifluoromethylation of unactivated alkenes using (TMS)CF3 (trimethyl(trifluoromethyl)silane) as the CF3 source is described. A broad range of electronically and structurally varied substrates undergo convenient and step-economical transformations for the concurrent construction of a five- or six-membered ring and a C-CF3 bond toward different types of trifluoromethyl azaheterocycles. The methodology not only circumvents use of expensive electrophilic CF3 reagents or the photoredox strategy but also expands the scope to substrates that are difficult to access by the existing methods. Mechanistic studies are conducted, and a plausible mechanism is proposed.
本文描述了首例以（三甲基（三氟甲基）硅烷）（TMS）CF₃为CF₃源，铜（I）催化未活化烯烃进行分子内氨基三氟甲基化反应。一系列电子结构多样的底物能够便捷且步骤经济地进行转化，用于同时构建五元或六元环以及C-CF₃键，以合成不同类型的三氟甲基氮杂环化合物。该方法不仅避免了使用昂贵的亲电CF₃试剂或光氧化还原策略，还将适用范围扩展到了现有方法难以实现的底物。开展了机理研究，并提出了一种合理的机理。
