Hypersensitive radical probes and the mechanisms of cytochrome P450-catalyzed hydroxylation reactions |
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Authors: | Newcomb M Toy P H |
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Affiliation: | Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA. |
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Abstract: | The title probes are precursors to kinetically calibrated, aryl-substituted cyclopropylcarbinyl radicals that rearrange with picosecond lifetimes. Applications in studies of cytochrome P450-catalyzed hydroxylation reactions are reviewed. Initially confusing results regarding lifetimes of radicals in the hydroxylation reactions were resolved when second-generation probes that distinguish between radicals and cations were employed. The results indicate that two electrophilic oxidizing species are involved in P450-catalyzed hydroxylations, an iron-oxo species that inserts oxygen and a hydroperoxo-iron species that inserts OH(+). The cationic rearrangement products are ascribed to reactions of the protonated alcohol products formed from the latter. |
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