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

Motohiro Fujiu; Kazuyuki Negishi; Jie Guang; Paul G Williard; Shigeki Kuroki; Koichi Mikami

doi:10.1039/c5dt03039k

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

Dalton Trans. 2015 Dec 7;44(45):19464-8. doi: 10.1039/c5dt03039k. Epub 2015 Oct 6.

Authors

Motohiro Fujiu¹, Kazuyuki Negishi, Jie Guang, Paul G Williard, Shigeki Kuroki, Koichi Mikami

Affiliation

¹ Department of Applied Chemistry, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8552, Japan. mikami.k.ab@m.titech.ac.jp.

PMID: 26440224
DOI: 10.1039/c5dt03039k

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 (1)H and (19)F DOSY analyses show that the addition of MAO and dioxane to the mixture of RFMgCl and Cp2ZrCl2 connects Cp2Zr and RFMg to generate the zirconocene/perfluoroalkyl-Grignard/dioxane complex.