Iron-catalyzed olefin cis-dihydroxylation by H2O2:: Electrophilic versus nucleophilic mechanisms

被引:114
作者
Fujita, M
Costas, M
Que, L
机构
[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
[2] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA
关键词
D O I
10.1021/ja029863d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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. Copyright © 2003 American Chemical Society.
引用
收藏
页码:9912 / 9913
页数:2
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