We report the facile
production of ArCF<sub>2</sub>X and ArCX<sub>3 </sub>from ArCF<sub>3</sub>
using catalytic iron(III)halides, which constitutes the first iron-catalyzed
halogen exchange for non-aromatic CF bonds. Theoretical calculations suggest direct activation of C–F bonds
by iron coordination. ArCX<sub>3</sub> and ArCF<sub>2</sub>X products of the reaction are synthetically valuable due to
their diversification potential. In particular, bromo-, chloro-, and
iododifluoromethyl arenes (ArCF<sub>2</sub>Br, ArCF<sub>2</sub>Cl, ArCF<sub>2</sub>I,
respectively) provide access to a myriad of difluoromethyl arene derivatives
(ArCF<sub>2</sub>R). To optimize for mono-halogen exchange, a statistical
method called Design of Experiments was used. Optimized parameters were
successfully applied to electron rich and electron deficient aromatic
substrates, and to the late stage diversification of flufenoxuron, a commercial
insecticide.