Xinrui Zhou

Doctoral Degree

大连理工大学

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Gender:Female
Business Address:西部校区化工实验楼E521
E-Mail:xinrui@dlut.edu.cn

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Evidence of Two Key Intermediates Contributing to the Selectivity of P450-Biomimetic Oxidation of Sulfides to Sulfoxides and Sulfones

Date of Publication:2012-10-01 Hits:

Indexed by:期刊论文
First Author:Zhou, Xinrui
Correspondence Author:Zhou, XR (reprint author), Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China.
Co-author:Chen, Xian,Jin, Yaqin,Marko, Istvan E.
Date of Publication:2012-10-01
Journal:CHEMISTRY-AN ASIAN JOURNAL
Included Journals:SCIE、EI、PubMed、Scopus
Volume:7
Issue:10
Page Number:2253-2257
ISSN No.:1861-4728
Key Words:biomimetic oxidation; porphyrin; reactive intermediates; sulfone; sulfoxide
Abstract: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.