Mechanistic Insight into the Aromatic Hydroxylation by High-Valent Iron(IV)-oxo Porphyrin π-Cation Radical Complexes

Mechanistic studies of the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radicals revealed that the aromatic oxidation involves an initial electrophilic attack on the π-system of the aromatic ring to produce a tetrahedral radical or cationic σ-complex. The mechanism was propo...

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Bibliographic Details
Published in:Journal of organic chemistry 2007-08, Vol.72 (16), p.6301-6304
Main Authors: Kang, Min-Jung, Song, Woon Ju, Han, Ah-Rim, Choi, Young S, Jang, Ho G, Nam, Wonwoo
Format: Article
Language:English
Subjects:
Cations
Chemistry
Chemistry, Organic - methods
Exact sciences and technology
Free radicals chemistry
Heterocyclic compounds
Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings
Iron - chemistry
Kinetics
Kinetics and mechanisms
Models, Chemical
Molecular Conformation
Organic chemistry
Porphyrins - chemistry
Preparations and properties
Reactivity and mechanisms
Spectrophotometry, Ultraviolet
Time Factors
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Summary:Mechanistic studies of the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radicals revealed that the aromatic oxidation involves an initial electrophilic attack on the π-system of the aromatic ring to produce a tetrahedral radical or cationic σ-complex. The mechanism was proposed on the basis of experimental results such as a large negative Hammett ρ value and an inverse kinetic isotope effect. By carrying out isotope labeling studies, the oxygen in oxygenated products was found to derive from the iron-oxo porphyrin intermediates.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo070557y