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高价铁（IV）-氧代卟啉π-阳离子自由基配合物催化芳烃羟基化反应的机理研究

Mechanistic insight into the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin pi-cation radical complexes.

作者信息

Kang Min-Jung, Song Woon Ju, Han Ah-Rim, Choi Young S, Jang Ho G, Nam Wonwoo

机构信息

Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.

出版信息

J Org Chem. 2007 Aug 3;72(16):6301-4. doi: 10.1021/jo070557y. Epub 2007 Jul 10.

DOI:10.1021/jo070557y
PMID:17622172
Abstract

Mechanistic studies of the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin pi-cation radicals revealed that the aromatic oxidation involves an initial electrophilic attack on the pi-system of the aromatic ring to produce a tetrahedral radical or cationic sigma-complex. The mechanism was proposed on the basis of experimental results such as a large negative Hammett rho 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.

摘要

高价铁（IV）-氧代卟啉π-阳离子自由基对芳烃羟基化的机理研究表明，芳烃氧化涉及对芳环π体系的初始亲电进攻，以生成四面体自由基或阳离子σ-络合物。该机理是基于诸如大的负哈米特ρ值和逆动力学同位素效应等实验结果提出的。通过进行同位素标记研究，发现氧化产物中的氧来自铁-氧代卟啉中间体。

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