Catalytic Aerobic Oxidation of Alkenes with Ferric Boroperoxo Porphyrin Complex; Reduction of Oxygen by Iron Porphyrin

We herein describe the development of a mild and selective catalytic aerobic oxidation process of olefins. This catalytic aerobic oxidation reaction was designed based on experimental and spectroscopic evidence assessing the reduction of atmospheric oxygen using a ferric porphyrin complex and pinacolborane to form a ferric boroperoxo porphyrin complex as an oxidizing species. The ferric boroperoxo porphyrin complex can be utilized as an in-situ generated intermediate in the catalytic aerobic oxidation of alkenes under ambient conditions to form oxidation products that differ from those obtained using previously reported ferric porphyrin catalysis. Moreover, the mild reaction conditions allow chemoselective oxidation to be achieved. We herein reported the first direct experimental evidence demonstrating that a ferric porphyrin complex can reduce atmospheric oxygen in the presence of HBpin to form a ferric boroperoxo porphyrin complex.