Photocatalytic Direct Deoxytrifluoromethoxylation of Phenols

We developed a photoredox strategy to achieve the deoxytrifluoromethoxylation of phenols. This approach leverages the propensity of the OCF₃ anion to decompose into difluorophosgene, which subsequently reacts <i>in situ</i> with phenol to form an aryl carbonofluoridate, thereby reducing the bond energy of the Csp²-O bond. The use of organic photoredox catalysts enables the operation of this method under mild conditions, with simple procedures and broad applicability to various phenolic substrates, and exhibits excellent selectivity among multiple C-O bonds.