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Title: Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins

Abstract

As a result of the adaptation of life to an aerobic environment, nature has evolved a panoply of metalloproteins for oxidative metabolism and protection against reactive oxygen species. Despite the diverse structures and functions of these proteins, they share common mechanistic grounds. An open-shell transition metal like iron or copper is employed to interact with O2 and its derived intermediates such as hydrogen peroxide to afford a variety of metal-oxygen intermediates. These reactive intermediates, including metal-superoxo, -(hydro)peroxo, and high-valent metal-oxo species, are the basis for the various biological functions of O2-utilizing metalloproteins. Collectively, these processes are called oxygen activation. Much of our understanding of the reactivity of these reactive intermediates has come from the study of hemecontaining proteins and related metalloporphyrin compounds. These studies not only have deepened our understanding of various functions of heme proteins, such as O2 storage and transport, degradation of reactive oxygen species, redox signaling, and biological oxygenation, etc., but also have driven the development of bioinorganic chemistry and biomimetic catalysis. In this review, we survey the range of O2 activation processes mediated by heme proteins and model compounds with a focus on recent progress in the characterization and reactivity of important iron-oxygen intermediates. Representative reactionsmore » initiated by these reactive intermediates as well as some context from prior decades will also be presented. We will discuss the fundamental mechanistic features of these transformations and delineate the underlying structural and electronic factors that contribute to the spectrum of reactivities that has been observed in nature as well as those that have been invented using these paradigms. Given the recent developments in biocatalysis for non-natural chemistries and the renaissance of radical chemistry in organic synthesis, we envision that new enzymatic and synthetic transformations will emerge based on the radical processes mediated by metalloproteins and their synthetic analogs.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States, Department of Chemistry, California Institute of Technology, Pasadena, California 91125, United States
  2. Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF); Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1415162
Alternate Identifier(s):
OSTI ID: 1508325
Grant/Contract Number:  
SC0001298
Resource Type:
Published Article
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Name: Chemical Reviews Journal Volume: 118 Journal Issue: 5; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huang, Xiongyi, and Groves, John T. Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.chemrev.7b00373.
Huang, Xiongyi, & Groves, John T. Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins. United States. https://doi.org/10.1021/acs.chemrev.7b00373
Huang, Xiongyi, and Groves, John T. Fri . "Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins". United States. https://doi.org/10.1021/acs.chemrev.7b00373.
@article{osti_1415162,
title = {Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins},
author = {Huang, Xiongyi and Groves, John T.},
abstractNote = {As a result of the adaptation of life to an aerobic environment, nature has evolved a panoply of metalloproteins for oxidative metabolism and protection against reactive oxygen species. Despite the diverse structures and functions of these proteins, they share common mechanistic grounds. An open-shell transition metal like iron or copper is employed to interact with O2 and its derived intermediates such as hydrogen peroxide to afford a variety of metal-oxygen intermediates. These reactive intermediates, including metal-superoxo, -(hydro)peroxo, and high-valent metal-oxo species, are the basis for the various biological functions of O2-utilizing metalloproteins. Collectively, these processes are called oxygen activation. Much of our understanding of the reactivity of these reactive intermediates has come from the study of hemecontaining proteins and related metalloporphyrin compounds. These studies not only have deepened our understanding of various functions of heme proteins, such as O2 storage and transport, degradation of reactive oxygen species, redox signaling, and biological oxygenation, etc., but also have driven the development of bioinorganic chemistry and biomimetic catalysis. In this review, we survey the range of O2 activation processes mediated by heme proteins and model compounds with a focus on recent progress in the characterization and reactivity of important iron-oxygen intermediates. Representative reactions initiated by these reactive intermediates as well as some context from prior decades will also be presented. We will discuss the fundamental mechanistic features of these transformations and delineate the underlying structural and electronic factors that contribute to the spectrum of reactivities that has been observed in nature as well as those that have been invented using these paradigms. Given the recent developments in biocatalysis for non-natural chemistries and the renaissance of radical chemistry in organic synthesis, we envision that new enzymatic and synthetic transformations will emerge based on the radical processes mediated by metalloproteins and their synthetic analogs.},
doi = {10.1021/acs.chemrev.7b00373},
journal = {Chemical Reviews},
number = 5,
volume = 118,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1021/acs.chemrev.7b00373

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