SELECTIVE OXIDATION OF SULFIDE BY ArIO—METALLOPORPHYRIN SYSTEM-AN ENZYME MODELS-OXIDATION
- 1 July 1983
- journal article
- research article
- Published by Taylor & Francis in Phosphorus and Sulfur and the Related Elements
- Vol. 16 (1-2) , 67-78
- https://doi.org/10.1080/03086648308077753
Abstract
Various sulfides are easily oxidized selectively to the corresponding sulfoxides in quantitative yields by iodosylarene (ArIO) catalyzed by metalloporphyrin (TPPM(III)Cl (M [dbnd] Fe, Mn)). The oxidation system is demonstrated to be a possible model for monooxygenase in the study of the stereochemistry of these sulfoxides. Metalloporphyrin-iodosylarene can initially equilibrate with the oxometalloporphyrin (TPPM(V)=O·Cl) formed in situ. The initial process may involve one-electron transfer from the sulfide to the intermediate oxometalloporphyrin followed by coupling of two resulting charged products, and/or nucleophilic attack of sulfide on oxometalloporphyrin oxygen. The overall reactions are depicted by paths with different electron demands from the results of Hammett plots.Keywords
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