SNAr catalysis enhanced by an aromatic donor–acceptor interaction; facile access to chlorinated polyfluoroarenes

Selective catalytic S_NAr reaction of polyfluoroaryl C-F bonds with chloride is shown. Stoichiometric TMSCl makes the reaction exergonic and allows catalysis, which involves ground state elevation of chloride, aromatic donor-acceptor interactions, and stabilization of the Meisenheimer complex. Traditional cross-coupling of the products is now possible and demonstrates the utility.