Department of Chemistry, South University of Science and Technology of China , Shenzhen 518055, China.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
J Am Chem Soc. 2016 Aug 3;138(30):9357-60. doi: 10.1021/jacs.6b04077. Epub 2016 Jul 20.
A novel asymmetric radical aminotrifluoromethylation of alkenes has been developed for the first time, providing straightforward access to densely functionalized CF3-containing azaheterocycles bearing an α-tertiary stereocenter with excellent enantioselectivity. The key to success is not only the introduction of a Cu(I)/chiral phosphoric acid dual-catalytic system but also the use of urea with two acidic N-H as both the nucleophile and directing group. The utility of this method is illustrated by facile transformations of the products into other important compounds useful in organic synthesis and medicinal chemistry.
首次开发了一种新型不对称自由基烯基三氟甲基化反应，为含有α-三级立体中心的稠合功能化含 CF3 的氮杂环提供了直接途径，具有优异的对映选择性。成功的关键不仅在于引入了 Cu(I)/手性磷酸双催化体系，还在于使用了具有两个酸性 N-H 的尿素作为亲核试剂和导向基团。该方法的实用性通过将产物转化为有机合成和药物化学中有用的其他重要化合物得到了证明。
