Abstract
Elucidation of the mechanisms of oxygen atom transfer reactions catalyzed by monooxygenase metalloenzymes has been a major challenge in the field of oxidation chemistry.1,2 Such enzymes catalyze aliphatic hydroxylation, olefin epoxidation, aromatic hydroxylation, heteroatom oxidation, and heteroatom dealkylation, with dioxygen as the oxidant. Intensive study of cytochrome P-450 enzymes,1 which contain heme at their active sites, and of metalloporphyrin model compounds has resulted in a proposed catalytic mechanism which involves a high-valent iron oxo porphyrin complex as a reactive intermediate. By contrast, the active sites of non-heme iron-containing monooxygenase enzymes and their mechanisms are not as fully characterized. In recent years, the chemistry of these latter enzymes has attracted the attention of both bioinorganic and biological chemists who have consequently been characterizing their active sites and attempting to understand the mechanisms of their oxygen atom transfer reactions by studying the enzymes directly as well as model systems.2,3
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Valentine, J.S., Nam, W., Ho, R.Y.N. (1993). Non-Porphyrin Iron Complex-Catalyzed Epoxidation of Olefins. In: Barton, D.H.R., Martell, A.E., Sawyer, D.T. (eds) The Activation of Dioxygen and Homogeneous Catalytic Oxidation. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3000-8_14
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DOI: https://doi.org/10.1007/978-1-4615-3000-8_14
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