Model systems for cytochrome P450 dependent mono-oxygenases. Part 3. The stereochemistry of hydroxylation of cis- and trans-decahydronaphthalene by chemical models for cytochrome P450 dependent mono-oxygenases

Abstract

The stereochemistry of hydroxylation of the tertiary C–H bonds of cis- and trans-decahydronaphthalene by seven chemical models for cytochrome P450 dependent mono-oxygenases has been studied. Oxidations by three of the model systems (H₂O₂–Fe²⁺–CH₃CN, O₂–Fe²⁺–2-mercaptobenzoic acid, and diazofluorene–hν–O₂) are non-stereospecific giving the same ratio of cis- to trans-decahydronaphthalen-9-ol from each substrate. However, hydroxylations with pyridine N-oxide–hν show a partial retention of configuration and with trifluoroperacetic acid or with iron(III) porphyrins and iodosylbenzene the oxidations are > 97% stereospecific. The mechanisms of these hydroxylations and their usefulness as models for the cytochrome P450 dependent mono-oxygenases are discussed.