Hypersensitive Radical Probes and the Mechanisms of Cytochrome P450-Catalyzed Hydroxylation Reactions
- 26 April 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 33 (7) , 449-455
- https://doi.org/10.1021/ar960058b
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.Keywords
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