State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Angew Chem Int Ed Engl. 2021 Jan 4;60(1):186-190. doi: 10.1002/anie.202010839. Epub 2020 Oct 29.
An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy) , visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.
已开发出一种涉及 1,2-芳基迁移的高效光催化乙烯基取代全碳季铵中心的全氟烷基化方法。重排反应使用 fac-Ir(ppy) 、可见光和市售的全氟烷基卤化物，并可以一步生成其他方法难以制备的有价值的多取代全氟烷基化化合物。从机理上讲，光诱导的烷基自由基加成到烯烃上导致相邻的全碳季铵中心上的偕二芳基取代基迁移，同时生成一个带有两个吸电子基团的 C-自由基，该自由基进一步被氢供体还原以完成多米诺序列。
