标题：
Evidence of Two Key Intermediates Contributing to the Selectivity of P450-Biomimetic Oxidation of Sulfides to Sulfoxides and Sulfones
点击次数：
论文类型：
期刊论文
发表刊物：
CHEMISTRY-AN ASIAN JOURNAL
收录刊物：
SCIE、EI、PubMed、Scopus
卷号：
7
期号：
10
页面范围：
2253-2257
ISSN号：
1861-4728
关键字：
biomimetic oxidation; porphyrin; reactive intermediates; sulfone;
sulfoxide
摘要：
A mild process for the selective oxidation of sulfides is in great demand. Therefore, probing the mechanism underlying the biological oxidation of sulfides under ambient conditions may provide valuable insights for the development of such a reaction. Based on porphyrin models of P450 enzymes, evidence of two key intermediates, Int0 and Int1, in this reaction is provided. Spectroscopic studies indicated the formation of a hydroperoxide-iron(III) species (Int0) upon addition of H2O2. This intermediate proved to be highly selective for sulfoxide production. By contrast, a defined porphyrin oxoiron(IV) cation radical (Int1) directly reacted with sulfoxides, leading selectively to the corresponding sulfones. Interestingly, the available sulfoxides reversibly act as a new axial ligand for Int0 forming a more active species Int0SO. The amount of Int0 increased in the presence of alkyl, aryl, or aromatic sulfides, while Int1 formed in the absence of these sulfides. Thus, sulfoxides and sulfones would selectively form under conditions that favor the corresponding intermediates, which elucidate the biological oxidation pathway.
发表时间：
2012-10-01
学位：博士
职称：副教授
学科：精细化工. 应用化学
所在单位：化工学院