Copper‐Catalyzed Hydroxylation of Simple Fluoroaryl and Aryl Chlorides: A Route to (Fluoro)phenols

A copper‐catalyzed conversion of polyfluoroaryl chlorides to the corresponding phenols was developed. A simple ligand system was applied, as well as potassium carbonate as an inexpensive and effective base, while significantly suppressing competing S N Ar pathways. The generality of the method was further demonstrated with simple aryl chlorides, which also underwent efficient hydroxylation. Mechanistic studies suggest that the reaction proceeds via a Cu(I)/Cu(III) catalytic cycle. Notably, the use of a sulfolane/water solvent system enabled high reactivity at a low catalyst loading, underscoring the practicality and scalability of this protocol.