Oxygen Activation by Iron(III)-Porphyrin/NaBH_4/Me_4N・OH System as Cytochrome P-450 Model. Oxygenation of Olefin, N-Dealkylation of Tertiary Amine, Oxidation of Sulfide, and Oxidative Cleavage of Ether Bond

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Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe^<3+>TPPCl), NaBH_4,Me_4N・OH, and molecular dioxygen in benzene-methanol solution. Fe^<3+>TPPCl, NaBH_4,and molecular dioxygen were essential for these reactions and the yields were decreased when Me_4N・OH was absent. Olefins were converted to alcohols, which were not produced from the corresponding epoxides under the same conditions. In styrene oxygenation, an electron-donating substituent on the substrate decreased the reactivity, whereas in N, N-dimethylaniline demethylation, it enhanced the reactivity. Despite the use of the same reagents, the key intermediates of these two reactions are different. Fe^<2+>TPP-σ-alkyl complexes produced from Fe^<3+>TPPCl, olefin, and NaBH_4 were identified as intermediates under anaerobic conditions. Fe^<2+>TPP-σ-alkyl complex reacted with molecular dioxygen to give oxygenated products.Examination of the relative reactivities of p-substituted N, N-dimethylanilines in the NaBH_4 reaction system revealed first, that the demethylation proceeded via one-electron abstraction, and second, that the reactive species of the demethylation reactions seems to be an iron-oxenoid.
公益社団法人日本薬学会の論文
1993-02-15