Bio-inspired Nonheme Iron Oxidation Catalysis: Involvement of Oxoiron(V) Oxidants in Cleaving Strong C−H Bonds

Subhasree Kal; Shuangning Xu; Lawrence Que

doi:10.1002/anie.201906551

Bio-inspired Nonheme Iron Oxidation Catalysis: Involvement of Oxoiron(V) Oxidants in Cleaving Strong C−H Bonds

Subhasree Kal, Shuangning Xu, Lawrence Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Review article › peer-review

112 Scopus citations

Abstract

Nonheme iron enzymes generate powerful and versatile oxidants that perform a wide range of oxidation reactions, including the functionalization of inert C−H bonds, which is a major challenge for chemists. The oxidative abilities of these enzymes have inspired bioinorganic chemists to design synthetic models to mimic their ability to perform some of the most difficult oxidation reactions and study the mechanisms of such transformations. Iron-oxygen intermediates like iron(III)-hydroperoxo and high-valent iron-oxo species have been trapped and identified in investigations of these bio-inspired catalytic systems, with the latter proposed to be the active oxidant for most of these systems. In this Review, we highlight the recent spectroscopic and mechanistic advances that have shed light on the various pathways that can be accessed by bio-inspired nonheme iron systems to form the high-valent iron-oxo intermediates.

Original language	English (US)
Pages (from-to)	7332-7349
Number of pages	18
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	19
DOIs	https://doi.org/10.1002/anie.201906551
State	Published - May 4 2020

Bibliographical note

Funding Information:
The efforts in my laboratory over the past twenty years to develop bio-inspired nonheme iron catalysts and shed light on the nature of high-valent nonheme iron oxidants have been supported by the US Department of Energy, the National Institutes of Health, the National Science Foundation and the University of Minnesota. Current research efforts in the Que laboratory are supported by the National Science Foundation (CHE-1665391) and the National Institutes of Health (R01 GM-38767 and R35 GM-131721). We also thank Prof. Yisong Guo for his helpful comments on the electronic structure of 9 a.

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

C−H bond cleavage
high-valent iron-oxo species
nonheme iron enzymes
oxidation catalysis

PubMed: MeSH publication types

Journal Article
Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.
Review

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10.1002/anie.201906551

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abstract = "Nonheme iron enzymes generate powerful and versatile oxidants that perform a wide range of oxidation reactions, including the functionalization of inert C−H bonds, which is a major challenge for chemists. The oxidative abilities of these enzymes have inspired bioinorganic chemists to design synthetic models to mimic their ability to perform some of the most difficult oxidation reactions and study the mechanisms of such transformations. Iron-oxygen intermediates like iron(III)-hydroperoxo and high-valent iron-oxo species have been trapped and identified in investigations of these bio-inspired catalytic systems, with the latter proposed to be the active oxidant for most of these systems. In this Review, we highlight the recent spectroscopic and mechanistic advances that have shed light on the various pathways that can be accessed by bio-inspired nonheme iron systems to form the high-valent iron-oxo intermediates.",

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Bio-inspired Nonheme Iron Oxidation Catalysis: Involvement of Oxoiron(V) Oxidants in Cleaving Strong C−H Bonds

Abstract

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Keywords

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