Mononuclear Nonheme High-Spin Iron(III)-Acylperoxo Complexes in Olefin Epoxidation and Alkane Hydroxylation Reactions

Journal of the American Chemical Society
Bin WangWonwoo Nam

Abstract

Mononuclear nonheme high-spin iron(III)-acylperoxo complexes bearing an N-methylated cyclam ligand were synthesized, spectroscopically characterized, and investigated in olefin epoxidation and alkane hydroxylation reactions. In the epoxidation of olefins, epoxides were yielded as the major products with high stereo-, chemo-, and enantioselectivities; cis- and trans-stilbenes were oxidized to cis- and trans-stilbene oxides, respectively. In the epoxidation of cyclohexene, cyclohexene oxide was formed as the major product with a kinetic isotope effect (KIE) value of 1.0, indicating that nonheme iron(III)-acylperoxo complexes prefer C═C epoxidation to allylic C-H bond activation. Olefin epoxidation by chiral iron(III)-acylperoxo complexes afforded epoxides with high enantioselectivity, suggesting that iron(III)-acylperoxo species, not high-valent iron-oxo species, are the epoxidizing agent. In alkane hydroxylation reactions, iron(III)-acylperoxo complexes hydroxylated C-H bonds as strong as those in cyclohexane at -40 °C, wherein (a) alcohols were yielded as the major products with high regio- and stereoselectivities, (b) activation of C-H bonds by the iron(III)-acylperoxo species was the rate-determining step with a large KIE val...Continue Reading

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Citations

Nov 24, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Georgiy B Shul'pinPolina M Tyubaeva
Mar 11, 2017·Chemical Reviews·Xiao-Song XueJin-Pei Cheng
Jan 27, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Giorgio OlivoMiquel Costas
Mar 25, 2017·Nature Communications·Bin WangWonwoo Nam
Oct 13, 2020·Angewandte Chemie·Arnab K MaityChristopher Uyeda
Dec 15, 2020·Chemical Society Reviews·Shunichi FukuzumiWonwoo Nam

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