Oxidative dealkylation of tertiary amines by iron(III) porphyrin-iodosoxylene system as a model of cytochrome P-450.

The oxidative dealkylation of several tertiary amines with 2-iodoso-m-xylene catalyzed by chloro-α, β, γ, δ-tetraphenylporphinatoiron (III) (Fe (III) TPPCl, 3) was examined. N, N-Dimethylaniline (2) was smoothly dealkylated to N-methylaniline (4) in mild conditions and 3 was ascertained to act as an effective catalyst in this system. N, N-Diethylaniline and N, N-dimethylbenzylamine were similarly dealkylated. When the oxidation of 2 was carried out in the presence of methanol, N-methoxymethyl-N-methylaniline was predominantly formed and the formation of 4 was suppressed. This result suggests that the reactive cationic species, iminium ion, is formed in this reaction. The possible mechanism of this biomimetic dealkylation is also discussed.