Selective Light-Driven Chemoenzymatic Trifluoromethylation/Hydroxylation of Substituted Arenes

The merging of photoredox trifluoromethylation with hybrid P450 BM3 variants has enabled the selective light-driven functionalization of several arenes. This approach capitalizes on the unique photochemical properties of the Ru(II)-diimine photosensitizer to initiate single electron transfer events. Under photoredox conditions, a CF3 radical promoted by the d6 metal complex can add to arenes. In the hybrid P450 BM3 enzymes, the covalently attached Ru(II)-diimine photosensitizer provides the necessary electrons to perform, upon visible light activation, P450 oxyfunctionalizations on the trifluoromethylated substrates.