Chemo-, regio-, and stereo-selective perfluoroalkylations by a Grignard complex with zirconocene

Abstract

The synthesis of highly reactive perfluoroalkyl Grignard reagents with early transition metal zirconocene complexes and their new types of highly chemo-, regio-, and stereo-selective perfluoroalkylation reactions are reported with epoxides in particular. The zirconocene complex is advantageous in activating the perfluoroalkyl Grignard species. The zirconocene·Grignard complexes were clarified by DOSY. Both ¹H and ¹⁹F DOSY analyses show that the addition of MAO and dioxane to the mixture of R_FMgCl and Cp₂ZrCl₂ connects Cp₂Zr and R_FMg to generate the zirconocene/perfluoroalkyl-Grignard/dioxane complex.