Oxygen activation by iron(III)-porphyrin/NaBH4/Me4N·OH system as cytochrome P-450 model. Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond

T. Mori, T. Santa, T. Higuchi, Tadahiko Mashino, M. Hirobe

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8 Citations (Scopus)

Abstract

Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·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. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+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 NaBH4 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.

Original languageEnglish
Pages (from-to)292-295
Number of pages4
JournalChemical and Pharmaceutical Bulletin
Volume41
Issue number2
Publication statusPublished - 1993
Externally publishedYes

Fingerprint

Dealkylation
Oxygenation
Porphyrins
Alkenes
Sulfides
Ether
Cytochrome P-450 Enzyme System
Amines
Iron
Chemical activation
Oxygen
Oxidation
Electrons
Styrene
Epoxy Compounds
Benzene
Methanol
Alcohols
Substrates
N,N-dimethylaniline

ASJC Scopus subject areas

  • Chemistry(all)
  • Organic Chemistry
  • Drug Discovery
  • Pharmacology

Cite this

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title = "Oxygen activation by iron(III)-porphyrin/NaBH4/Me4N·OH system as cytochrome P-450 model. Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond",
abstract = "Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·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. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+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 NaBH4 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.",
author = "T. Mori and T. Santa and T. Higuchi and Tadahiko Mashino and M. Hirobe",
year = "1993",
language = "English",
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T1 - Oxygen activation by iron(III)-porphyrin/NaBH4/Me4N·OH system as cytochrome P-450 model. Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond

AU - Mori, T.

AU - Santa, T.

AU - Higuchi, T.

AU - Mashino, Tadahiko

AU - Hirobe, M.

PY - 1993

Y1 - 1993

N2 - Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·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. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+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 NaBH4 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.

AB - Oxygenation of olefin, N-dealkylation of tertiary amine, oxidation of sulfide, and oxidative cleavage of ether bond were conducted with tetraphenylporphyrinatoiron(III) (Fe3+TPPCl), NaBH4, Me4N·OH, and molecular dioxygen in benzene-methanol solution. Fe3+TPPCl, NaBH4, and molecular dioxygen were essential for these reactions and the yields were decreased when Me4N·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. Fe2+TPP-σ-alkyl complexes produced from Fe3+TPPCl, olefin, and NaBH4 were identified as intermediates under anaerobic conditions. Fe2+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 NaBH4 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.

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