Epoxidation of olefins by cytochrome P-450 model compounds: mechanism of oxygen atom transfer.
The mechanism of the Mn(III) porphyrin-catalyzed epoxidation of olefins by lithium hypochlorite is examined. The active oxidant is thought to be a high-valent manganese-oxo complex. It is shown that a relatively stable intermediate is reversibly formed upon interaction of the olefin and the oxo complex. The decomposition of this intermediate to Mn(III) porphyrin and epoxide is the rate-determining step of the catalytic cycle. Some analogies to the biochemical epoxidation of olefins catalyzed by cytochrome P-450 are discussed.
D000475:Alkenes; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism*; D004852:Epoxy Compounds; D004988:Ethers, Cyclic; D007202:Indicators and Reagents; D007700:Kinetics; D008345:Manganese; D008665:Metalloporphyrins; D008954:Models, Biological; D010084:Oxidation-Reduction
D000475:Alkenes; D004852:Epoxy Compounds; D004988:Ethers, Cyclic; D007202:Indicators and Reagents; D008665:Metalloporphyrins; C041471:manganese tetraphenylporphyrin; D008345:Manganese; D003577:Cytochrome P-450 Enzyme System