Formation of Iron(III) meso-Chloro-isoporphyrin as a Reactive Chlorinating Agent from Oxoiron(IV) Porphyrin π-Cation Radical
Formation of Iron(III) meso-Chloro-isoporphyrin as a Reactive Chlorinating Agent from Oxoiron(IV) Porphyrin π-Cation Radical
复制标题
DOI：
10.1021/ja209985v
复制
发表时间：
2012-03-14
影响因子：
15
通讯作者：
Fujii, Hiroshi
中科院分区：
文献类型：
--
作者：
Cong, Zhiqi;Kurahashi, Takuya;Fujii, Hiroshi
铁（III）异卟啉是卟啉与饱和的中间位碳的互变异构体，是氧代铁（IV）卟啉π-阳离子自由基的等电子形式之一，是多种血红素酶的重要反应中间体。异卟啉被认为不能催化氧化和氧化反应。在这里，我们报告的氧代铁（IV）卟啉π-阳离子自由基可以转化为铁（III）meso-氯-异卟啉在三氟乙酸和氯离子的存在下。更重要的是，这项研究表明，铁（III）meso-chloro-isoporphyrin是一个很好的反应剂氯化芳香族化合物和烯烃的第一个证据。本研究的结果表明，该机制涉及亲电氯化的基板与铁（III）meso-chloro-isoporphyrin。
Iron(III) isoporphyrin, a tautomer of porphyrin with a saturated meso carbon, is one of the isoelectronic forms of oxoiron(IV) porphyrin pi-cation radical, which is known as an important reactive intermediate of various heme enzymes. The isoporphyrin has been believed to be incapable of catalyzing oxygenation and oxidation reactions. Here, we report that an oxoiron(IV) porphyrin pi-cation radical can be converted to iron(III) meso-chloro-isoporphyrin in the presence of trifluoroacetic acid and chloride ion. More importantly, this study shows the first evidence that iron(III) meso-chloro-isoporphyrin is an excellent reactive agent for chlorinating aromatic compounds and olefins. The results of this study suggest that the mechanism involves electrophilic chlorination of substrate with iron(III) meso-chloro-isoporphyrin.