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

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

Research output: Contribution to journalArticle

21 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)1455-1460
Number of pages6
JournalAdvanced Synthesis and Catalysis
Volume352
Issue number9
DOIs
Publication statusPublished - 1 Jun 2010
Externally publishedYes

Keywords

  • Catalysis
  • Hypervalent iodine
  • Iodine
  • Oxidation
  • Porphyrinoids

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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