Ferric chloride-catalyzed activation of hydrogen peroxide for the demethylation of N,N-dimethylaniline, the epoxidation of olefins, and the oxidative cleavage of vicinal diols in acetonitrile: a reaction mimic for cytochrome P-450.

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Abstract
In dry acetonitrile, anhydrous FeIIICl3 catalyzes the demethylation of N,N-dimethylaniline, the epoxidation of olefins, and the oxidative cleavage of 1-phenyl-1,2-ethanediol (and other 1,2-diols) by hydrogen peroxide. For each class of substrate the products closely parallel those that result from their enzymatic oxidation by cytochrome P-450. Because of (i) the close congruence of products, (ii) the catalytic nature of the FeIIICl3/H2O2 reaction mimic, and (iii) the similarity of the dipolar aprotic solvent (acetonitrile) to the proteinaceous lipid matrix of the biomembrane, the form of the reactive intermediate may be the same in each case. A mechanism is proposed in which an iniital Lewis acid-base interaction of FeIIICl3 with H2O2 generates a highly electrophilic FeIII-oxene species as the reactive intermediate. This is in contrast to the prevailing view that cytochrome P-450 acts as a redox catalyst to generate an FeV-oxo species or an FeIV-oxo cation radical as the reactive intermediate.

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