Metalloporphyrin/Iodine(III)-Cocatalyzed oxygenation of aromatic hydrocarbons asc.wiley-vch.de

Akira Yoshimura, Heather M. Neu, Victor N. Nemykin, Viktor V. Zhdankin

Результат исследований: Материалы для журналаСтатья

20 Цитирования (Scopus)

Выдержка

Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol% of iodobenzene and 5 mol% of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.

Язык оригиналаАнглийский
Страницы (с-по)1455-1460
Число страниц6
ЖурналAdvanced Synthesis and Catalysis
Том352
Номер выпуска9
DOI
СостояниеОпубликовано - 1 июн 2010
Опубликовано для внешнего пользованияДа

Отпечаток

Metalloporphyrins
Aromatic Hydrocarbons
Oxygenation
Aromatic hydrocarbons
Iodine
Porphyrins
Oxidation
Cations
Iron
Positive ions
Anthraquinones
Styrene
Epoxidation
Anthracene
Catalytic oxidation
Acetonitrile
Ions
iodobenzene
Water

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Цитировать

Metalloporphyrin/Iodine(III)-Cocatalyzed oxygenation of aromatic hydrocarbons asc.wiley-vch.de. / Yoshimura, Akira; Neu, Heather M.; Nemykin, Victor N.; Zhdankin, Viktor V.

В: Advanced Synthesis and Catalysis, Том 352, № 9, 01.06.2010, стр. 1455-1460.

Результат исследований: Материалы для журналаСтатья

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abstract = "Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol{\%} of iodobenzene and 5 mol{\%} of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol{\%} of iodobenzene. The oxidation of styrene in the presence of 20 mol{\%} of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.",
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N2 - Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol% of iodobenzene and 5 mol% of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.

AB - Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol% of iodobenzene and 5 mol% of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.

KW - Catalysis

KW - Hypervalent iodine

KW - Iodine

KW - Oxidation

KW - Porphyrinoids

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