Iron-Catalyzed Highly para-Selective Difluoromethylation of Arenes

J Am Chem Soc. 2020 Dec 9;142(49):20524-20530. doi: 10.1021/jacs.0c09545. Epub 2020 Nov 30.

Abstract

Direct functionalization of a C-H bond at either the meta or para position by only changing the catalyst system poses a significant challenge. We herein report the [Fe(TPP)Cl]-enabled, selective, C-H difluoromethylation of arenes using BrCF2CO2Et as the difluoromethylation source, which successfully altered the selectivity from the meta to the para position. A preliminary mechanistic study revealed the iron porphyrin complex not only activated the aromatic ring but also induced para selectivity due to the influence of ligand sterics.