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Evidence of Two Key Intermediates Contributing to the Selectivity of P450‐Biomimetic Oxidation of Sulfides to Sulfoxides and Sulfones
Author(s) -
Zhou Xinrui,
Chen Xian,
Jin Yaqin,
Markó Istvan E.
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201200422
Subject(s) - sulfoxide , chemistry , porphyrin , aryl , selectivity , alkyl , reactive intermediate , reaction intermediate , ligand (biochemistry) , combinatorial chemistry , organic chemistry , catalysis , biochemistry , receptor
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 H 2 O 2 . 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 Int0 SO . 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.