Iron-catalyzed olefin cis-dihydroxylation by H2O2: electrophilic versus nucleophilic mechanisms |
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Authors: | Fujita Megumi Costas Miquel Que Lawrence |
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Affiliation: | Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA. |
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Abstract: | Previous studies have classified a series of nonheme iron catalysts for olefin cis-dihydroxylation by H2O2 into two groups. Complex 1, [(TPA)Fe(OTf)2], representative of Class A catalysts, forms a low-spin FeIII-OOH intermediate that gives rise to a high-valent FeV(=O)OH oxidant. The preference of this catalyst for electron-rich olefins demonstrates its electrophilic character. On the other hand, complex 2, [(6-Me3-TPA)Fe(OTf)2], representative of Class B catalysts, prefers instead to oxidize electron-deficient olefins, suggesting an oxidant with nucleophilic character. It is suggested that such a nucleophilic oxidant may be the high-spin FeIII-OOH intermediate derived from 2 or the FeIV(=O)(*OH) species derived therefrom. |
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