Room Temperature Regioselective Catalytic Hydrodefluorination of Fluoroarenes with trans-[Ru(NHC)4 H2 ] through a Concerted Nucleophilic Ru-H Attack Pathway

Mateusz K Cybulski; David McKay; Stuart A Macgregor; Mary F Mahon; Michael K Whittlesey

doi:10.1002/anie.201610820

Room Temperature Regioselective Catalytic Hydrodefluorination of Fluoroarenes with trans-[Ru(NHC)₄ H₂ ] through a Concerted Nucleophilic Ru-H Attack Pathway

Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1515-1519. doi: 10.1002/anie.201610820. Epub 2017 Jan 9.

Authors

Mateusz K Cybulski¹, David McKay², Stuart A Macgregor², Mary F Mahon¹, Michael K Whittlesey¹

Affiliations

¹ Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
² Institute of Chemical Sciences, Heriot Watt University, Edinburgh, EH14 4AS, UK.

PMID: 28067455
DOI: 10.1002/anie.201610820

Abstract

The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe₄ )₄ H₂ ] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

Keywords: N-heterocyclic carbenes; density functional calculations; homogeneous catalysis; hydrodefluorination; ruthenium.

Publication types

Research Support, Non-U.S. Gov't