Utilising Sodium-Mediated Ferration for Regioselective Functionalisation of Fluoroarenes via C-H and C-F Bond Activations

DOI: 10.1002/anie.201709750

Authors: Eva Hevia (University of Strathclyde) , Lewis C. H. Maddock (lewis.maddock@strath.ac.uk) , Tracy Nixon (University of Strathclyde) , Alan R. Kennedy (University of Strathclyde) , Michael R. Probert (Newcastle University) , William Clegg (Newcastle University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition , VOL 57 , PAGES 187-191

State: Published (Approved)
Published: October 2017
Diamond Proposal Number(s): 11145

Abstract: While Fe(II) complexes have shown little promise in deprotonative metallation chemistry, pairing iron bis(amide) Fe(HMDS)2 with Na(HMDS) to form new sodium ferrate base [(dioxane)0.5·NaFe(HMDS)3] (1) enables regioselective mono and di-ferration (via direct Fe-H exchange) of a wide range of fluoroaromatic substrates under mild reaction conditions. Trapping of several ferrated intermediates has provided key insight into how synchronised Na/Fe cooperation operates in these transformations. Furthermore using excess 1 at 80oC switches on a remarkable cascade process inducing the collective 2-fold C-H/3-fold C-F bond activation, where each C-H bond is transformed to C-Fe bonds whereas each C-F bond is transformed into a C-N bond.

Journal Keywords: metallation; mixed-metal chemistry; C-F bond activation; cascade processes; ferrates

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction