Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols: A new manifestation of template catalysis

We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H⁺ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination.