Origin of the Oxygen Atom in C-H Bond Oxidations Catalyzed by a Water-Soluble Metalloporphyrin.

The monopersulfate oxidation of 4-isopropylbenzoic acid performed in H(2)(18)O and catalyzed by a water-soluble metalloporphyrin indicated that half of the oxygen atoms incorporated in 4-(1-hydroxy-1-methylethyl)benzoic acid, the primary hydroxylation product, came from water. A redox tautomerism of the active high-valent hydroxo-metal-oxo porphyrin intermediate coupled with an oxygen rebound mechanism explained this result. Under similar conditions, ketoprofen was directly oxidized to 3-benzoylacetophenone, via at least two different reaction pathways. Trapping of radical intermediates by molecular oxygen competed with the oxygen rebound mechanism.