Department of Chemistry and Winship Cancer Institute, Emory University , Atlanta, Georgia 30322, United States.
J Am Chem Soc. 2018 Jan 10;140(1):163-166. doi: 10.1021/jacs.7b12590. Epub 2017 Dec 26.
We describe a new catalytic approach to selective functionalization of the strong C-F bonds in trifluoromethylaromatic (Ar-CF) systems. In this approach, single electron reduction of Ar-CF substrates (using a photoredox catalyst) results in difluorobenzylic radical formation through a C-F cleavage mechanism. These radicals undergo efficient intermolecular coupling with simple alkenes in a defluoroalkylation process where radical termination is accomplished by a polarity reversal catalyst. This mild catalytic protocol engages a wide range of substrates to give medicinally relevant fluorinated substructures with complete regiocontrol.
我们描述了一种新的催化方法，用于三氟甲基芳基（Ar-CF）体系中强 C-F 键的选择性功能化。在这种方法中，通过光氧化还原催化剂对 Ar-CF 底物进行单电子还原，通过 C-F 断裂机制生成二氟苄基自由基。这些自由基通过 defluoroalkylation 过程与简单的烯烃进行高效的分子间偶联，其中自由基终止是通过极性反转催化剂完成的。这种温和的催化方案涉及广泛的底物，可提供具有完全区域选择性的具有药用相关性的氟化亚结构。
