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Title: Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation

Abstract

Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R–H) by high-valent iron-oxo species (Fe n=O) generates a substrate radical and a reduced iron hydroxide, [Fe n-1–OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R–OH, rebound to a non-oxygen atom affording R–X, electron transfer of the incipient radical to yield a carbocation, R +, desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C–H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C–H transformations are selected to illustrate how the behaviors ofmore » the radical pair [Fe n-1–OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of “radical rebound” processes as a general paradigm for developing novel C–H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic “radical rebound” with synthetic organic chemistry.« less

Authors:
 [1];  [1]
  1. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1397173
Grant/Contract Number:  
SC0001298
Resource Type:
Accepted Manuscript
Journal Name:
JBIC Journal of Biological Inorganic Chemistry
Additional Journal Information:
Journal Volume: 22; Journal Issue: 2-3; Related Information: CCHF partners with University of Virginia (lead); Brigham Young University; California Institute of Technology; Colorado School of Mines; University of Maryland; University of North Carolina, Chapel Hill; University of North Texas; Princeton University; The Scripps Research Institute; Yale University; Journal ID: ISSN 0949-8257
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huang, Xiongyi, and Groves, John T. Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation. United States: N. p., 2016. Web. doi:10.1007/s00775-016-1414-3.
Huang, Xiongyi, & Groves, John T. Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation. United States. doi:10.1007/s00775-016-1414-3.
Huang, Xiongyi, and Groves, John T. Thu . "Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation". United States. doi:10.1007/s00775-016-1414-3. https://www.osti.gov/servlets/purl/1397173.
@article{osti_1397173,
title = {Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation},
author = {Huang, Xiongyi and Groves, John T.},
abstractNote = {Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R–H) by high-valent iron-oxo species (Fen=O) generates a substrate radical and a reduced iron hydroxide, [Fen-1–OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R–OH, rebound to a non-oxygen atom affording R–X, electron transfer of the incipient radical to yield a carbocation, R+, desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C–H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C–H transformations are selected to illustrate how the behaviors of the radical pair [Fen-1–OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of “radical rebound” processes as a general paradigm for developing novel C–H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic “radical rebound” with synthetic organic chemistry.},
doi = {10.1007/s00775-016-1414-3},
journal = {JBIC Journal of Biological Inorganic Chemistry},
number = 2-3,
volume = 22,
place = {United States},
year = {2016},
month = {12}
}

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Figures / Tables:

Fig. 1 Fig. 1: A variety of biotransformations catalyzed by iron-containing oxygenases and their mechanistic features

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Works referenced in this record:

Detection and Characterization of an Oxomanganese(V) Porphyrin Complex by Rapid-Mixing Stopped-Flow Spectrophotometry
journal, July 1997

  • Groves, John T.; Lee, Jinbo; Marla, Sudhakar S.
  • Journal of the American Chemical Society, Vol. 119, Issue 27
  • DOI: 10.1021/ja962605u

Selective oxygen transfer catalysed by heme peroxidases: synthetic and mechanistic aspects
journal, December 2000


Reaction of HppE with Substrate Analogues: Evidence for Carbon–Phosphorus Bond Cleavage by a Carbocation Rearrangement
journal, May 2013

  • Chang, Wei-chen; Mansoorabadi, Steven O.; Liu, Hung-wen
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja403441x

CAS MCSCF/CAS MCQDPT2 Study of the Mechanism of Singlet Oxygen Addition to 1,3-Butadiene and Benzene
journal, August 2000

  • Bobrowski, Maciej; Liwo, Adam; Ołdziej, Stanisław
  • Journal of the American Chemical Society, Vol. 122, Issue 34
  • DOI: 10.1021/ja001185c

Catalysis of Radical Reactions: A Radical Chemistry Perspective
journal, October 2015

  • Studer, Armido; Curran, Dennis P.
  • Angewandte Chemie International Edition, Vol. 55, Issue 1
  • DOI: 10.1002/anie.201505090

Mechanistic Consequences of Chiral Radical Clock Probes: Analysis of the Mononuclear Non-Heme Iron Enzyme HppE with 2-Hydroxy-3-methylenecyclopropyl Radical Clock Substrates
journal, February 2014

  • Huang, Hui; Chang, Wei-Chen; Lin, Geng-Min
  • Journal of the American Chemical Society, Vol. 136, Issue 8
  • DOI: 10.1021/ja4100035

High-valent iron in chemical and biological oxidations
journal, April 2006


Hydroxylation by cytochrome P-450 and metalloporphyrin models. Evidence for allylic rearrangement
journal, April 1984

  • Groves, John T.; Adhyam, Durga V.
  • Journal of the American Chemical Society, Vol. 106, Issue 7
  • DOI: 10.1021/ja00319a044

Chameleon States: High-Valent Metal-Oxo Species of Cytochrome P450 and Its Ruthenium Analogue
journal, August 2001


Unusual Kinetic Stability of a Ground-State Singlet Oxomanganese(V) Porphyrin. Evidence for a Spin State Crossing Effect
journal, March 1999

  • Jin, Ning; Groves, John T.
  • Journal of the American Chemical Society, Vol. 121, Issue 12
  • DOI: 10.1021/ja984429q

Radical Intermediates in Monooxygenase Reactions of Rieske Dioxygenases
journal, March 2007

  • Chakrabarty, Sarmistha; Austin, Rachel N.; Deng, Dayi
  • Journal of the American Chemical Society, Vol. 129, Issue 12
  • DOI: 10.1021/ja068188v

Synthesis and molecular structure of a nitrido(porphyrinato)chromium(V) complex
journal, March 1983

  • Groves, John T.; Takahashi, Tadashi; Butler, William M.
  • Inorganic Chemistry, Vol. 22, Issue 6
  • DOI: 10.1021/ic00148a009

Mechanism of Oxidation Reactions Catalyzed by Cytochrome P450 Enzymes
journal, September 2004

  • Meunier, Bernard; de Visser, Samuël P.; Shaik, Sason
  • Chemical Reviews, Vol. 104, Issue 9
  • DOI: 10.1021/cr020443g

Manganese-Catalyzed Late-Stage Aliphatic C–H Azidation
journal, April 2015

  • Huang, Xiongyi; Bergsten, Tova M.; Groves, John T.
  • Journal of the American Chemical Society, Vol. 137, Issue 16
  • DOI: 10.1021/jacs.5b01983

Iron-Catalyzed Reactions in Organic Synthesis
journal, December 2004

  • Bolm, Carsten; Legros, Julien; Le Paih, Jacques
  • Chemical Reviews, Vol. 104, Issue 12
  • DOI: 10.1021/cr040664h

When C–H bond functionalization meets visible-light photoredox catalysis
journal, January 2014


Substrate positioning controls the partition between halogenation and hydroxylation in the aliphatic halogenase, SyrB2
journal, October 2009

  • Matthews, M. L.; Neumann, C. S.; Miles, L. A.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 42
  • DOI: 10.1073/pnas.0909649106

Electronic Structure and Reactivity of Isomeric Oxo-Mn(V) Porphyrins:  Effects of Spin-State Crossing and p K a Modulation
journal, May 2006

  • De Angelis, Filippo; Jin, Ning; Car, Roberto
  • Inorganic Chemistry, Vol. 45, Issue 10
  • DOI: 10.1021/ic060306s

The medicinal chemist's toolbox for late stage functionalization of drug-like molecules
journal, January 2016

  • Cernak, Tim; Dykstra, Kevin D.; Tyagarajan, Sriram
  • Chemical Society Reviews, Vol. 45, Issue 3
  • DOI: 10.1039/C5CS00628G

Catalytic hydroxylation of saturated hydrocarbons with the sodium hypohalite/manganese porphyrin system
journal, July 1985


Hydroxylation of Camphor by Reduced Oxy-Cytochrome P450cam:  Mechanistic Implications of EPR and ENDOR Studies of Catalytic Intermediates in Native and Mutant Enzymes
journal, February 2001

  • Davydov, Roman; Makris, Thomas M.; Kofman, Victoria
  • Journal of the American Chemical Society, Vol. 123, Issue 7
  • DOI: 10.1021/ja003583l

Profiling Mechanisms of Alkane Hydroxylase Activity In Vivo Using the Diagnostic Substrate Norcarane
journal, February 2007


Hydroxylation and epoxidation catalyzed by iron-porphine complexes. Oxygen transfer from iodosylbenzene
journal, February 1979

  • Groves, John T.; Nemo, Thomas E.; Myers, Richard S.
  • Journal of the American Chemical Society, Vol. 101, Issue 4
  • DOI: 10.1021/ja00498a040

The Fenton oxidation mechanism: reactivities of biologically relevant substrates with two oxidizing intermediates differ from those predicted for the hydroxyl radical.
journal, July 1994

  • Wink, D. A.; Nims, R. W.; Saavedra, J. E.
  • Proceedings of the National Academy of Sciences, Vol. 91, Issue 14
  • DOI: 10.1073/pnas.91.14.6604

Mechanism of Oxygen Activation in a Flavin-Dependent Monooxygenase: A Nearly Barrierless Formation of C4a-Hydroperoxyflavin via Proton-Coupled Electron Transfer
journal, July 2015

  • Visitsatthawong, Surawit; Chenprakhon, Pirom; Chaiyen, Pimchai
  • Journal of the American Chemical Society, Vol. 137, Issue 29
  • DOI: 10.1021/jacs.5b04328

Mössbauer effect study of tight spin coupling in oxidized chloro‐5,10,15,20‐tetra(mesityl)porphyrinatoiron(III)
journal, August 1983

  • Boso, Brian; Lang, George; McMurry, Thomas J.
  • The Journal of Chemical Physics, Vol. 79, Issue 3
  • DOI: 10.1063/1.445913

Organometallic alkane CH activation
journal, November 2004


The“Rebound Controversy”: An Overview and Theoretical Modeling of the Rebound Step in C−H Hydroxylation by Cytochrome P450
journal, January 2004

  • Shaik, Sason; Cohen, Shimrit; de Visser, Samuël P.
  • European Journal of Inorganic Chemistry, Vol. 2004, Issue 2
  • DOI: 10.1002/ejic.200300448

Decarboxylation of Fatty Acids to Terminal Alkenes by Cytochrome P450 Compound I
journal, April 2015

  • Grant, Job L.; Hsieh, Chun H.; Makris, Thomas M.
  • Journal of the American Chemical Society, Vol. 137, Issue 15
  • DOI: 10.1021/jacs.5b01965

Solvent-Dependent Cage Dynamics of Small Nonpolar Radicals: Lessons from the Photodissociation and Geminate Recombination of Alkylcobalamins
journal, July 2009

  • Stickrath, Andrew B.; Carroll, Elizabeth C.; Dai, Xiaochuan
  • The Journal of Physical Chemistry A, Vol. 113, Issue 30
  • DOI: 10.1021/jp9017986

Aliphatic hydroxylation catalyzed by iron porphyrin complexes
journal, September 1983

  • Groves, John T.; Nemo, Thomas E.
  • Journal of the American Chemical Society, Vol. 105, Issue 20
  • DOI: 10.1021/ja00358a009

Driving Force for Oxygen-Atom Transfer by Heme-Thiolate Enzymes
journal, July 2013

  • Wang, Xiaoshi; Peter, Sebastian; Ullrich, René
  • Angewandte Chemie International Edition, Vol. 52, Issue 35
  • DOI: 10.1002/anie.201302137

E.s.r. evidence for chromium (V) porphyrinates
journal, January 1981

  • Groves, John T.; Haushalter, Robert C.
  • Journal of the Chemical Society, Chemical Communications, Issue 22
  • DOI: 10.1039/c39810001165

Undirected, Homogeneous C–H Bond Functionalization: Challenges and Opportunities
journal, May 2016


Using push to get pull
journal, January 2014


18 F-Labeling of Arenes and Heteroarenes for Applications in Positron Emission Tomography
journal, January 2016


Structural modeling of iron halogenases: synthesis and reactivity of halide-iron( iv )-oxo compounds
journal, January 2014

  • Planas, Oriol; Clémancey, Martin; Latour, Jean-Marc
  • Chemical Communications, Vol. 50, Issue 74
  • DOI: 10.1039/C4CC03234A

Mechanism of the Third Oxidative Step in the Conversion of Androgens to Estrogens by Cytochrome P450 19A1 Steroid Aromatase
journal, October 2014

  • Yoshimoto, Francis K.; Guengerich, F. Peter
  • Journal of the American Chemical Society, Vol. 136, Issue 42
  • DOI: 10.1021/ja508185d

X-ray absorption spectroscopy of chloroperoxidase compound I: Insight into the reactive intermediate of P450 chemistry
journal, November 2005

  • Stone, K. L.; Behan, R. K.; Green, M. T.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 46
  • DOI: 10.1073/pnas.0507069102

Theoretical Perspective on the Structure and Mechanism of Cytochrome P450 Enzymes
journal, June 2005

  • Shaik, Sason; Kumar, Devesh; de Visser, Samuël P.
  • Chemical Reviews, Vol. 105, Issue 6
  • DOI: 10.1021/cr030722j

High-valent ruthenium(IV) and -(VI) oxo complexes of octaethylporphyrin. Synthesis, spectroscopy, and reactivities
journal, November 1989

  • Leung, Wa Hung; Che, Chi Ming
  • Journal of the American Chemical Society, Vol. 111, Issue 24
  • DOI: 10.1021/ja00206a007

Modeling Non-Heme Iron Halogenases: High-Spin Oxoiron(IV)–Halide Complexes That Halogenate C–H Bonds
journal, February 2016

  • Puri, Mayank; Biswas, Achintesh N.; Fan, Ruixi
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11511

Chloroperoxidase compound I: electron paramagnetic resonance and Moessbauer studies
journal, December 1984

  • Rutter, Rick; Hager, Lowell P.; Dhonau, Howard
  • Biochemistry, Vol. 23, Issue 26
  • DOI: 10.1021/bi00321a082

Mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad: recent developments in enzymology and modeling studies
journal, January 2008

  • Bruijnincx, Pieter C. A.; van Koten, Gerard; Klein Gebbink, Robertus J. M.
  • Chemical Society Reviews, Vol. 37, Issue 12
  • DOI: 10.1039/b707179p

pH-induced mechanistic changeover from hydroxyl radicals to iron(iv) in the Fenton reaction
journal, January 2012

  • Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja
  • Chemical Science, Vol. 3, Issue 5
  • DOI: 10.1039/c2sc20099f

Direct nitration and azidation of aliphatic carbons by an iron-dependent halogenase
journal, January 2014

  • Matthews, Megan L.; Chang, Wei-chen; Layne, Andrew P.
  • Nature Chemical Biology, Vol. 10, Issue 3
  • DOI: 10.1038/nchembio.1438

Analysis of Reaction Channels for Alkane Hydroxylation by Nonheme Iron(IV)-Oxo Complexes
journal, July 2010

  • Geng, Caiyun; Ye, Shengfa; Neese, Frank
  • Angewandte Chemie International Edition, Vol. 49, Issue 33
  • DOI: 10.1002/anie.201001850

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics
journal, November 2010


Dioxygen Activation at Mononuclear Nonheme Iron Active Sites:  Enzymes, Models, and Intermediates
journal, February 2004

  • Costas, Miquel; Mehn, Mark P.; Jensen, Michael P.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020628n

PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View
journal, June 2004


The rebound mechanism in catalytic C–H oxidation by MnO(tpp)Cl from DFT studies: electronic nature of the active species
journal, January 2008

  • Balcells, David; Raynaud, Christophe; Crabtree, Robert H.
  • Chem. Commun., Issue 6
  • DOI: 10.1039/B715939K

A Highly Reactive P450 Model Compound I
journal, July 2009

  • Bell, Seth R.; Groves, John T.
  • Journal of the American Chemical Society, Vol. 131, Issue 28
  • DOI: 10.1021/ja903394s

Hydrocarbon oxidations with oxometalloporphinates. Isolation and reactions of a (porphinato)manganese(V) complex
journal, September 1980

  • Groves, John T.; Kruper, William J.; Haushalter, Robert C.
  • Journal of the American Chemical Society, Vol. 102, Issue 20
  • DOI: 10.1021/ja00540a050

Late Stage Azidation of Complex Molecules
journal, October 2016


Making and Breaking the Dioxygen O−O Bond:  New Insights from Studies of Synthetic Copper Complexes
journal, June 1997

  • Tolman, William B.
  • Accounts of Chemical Research, Vol. 30, Issue 6
  • DOI: 10.1021/ar960052m

Effects of a thiolate axial ligand on the π→π* electronic states of oxoferryl porphyrins: a study of the optical and resonance Raman spectra of compounds I and II of chloroperoxidase
journal, January 2001

  • Egawa, Tsuyoshi; Proshlyakov, Denis A.; Miki, Hideho
  • JBIC Journal of Biological Inorganic Chemistry, Vol. 6, Issue 1
  • DOI: 10.1007/s007750000181

Timing of the radical recombination step in cytochrome P-450 catalysis with ring-strained probes
journal, May 1987

  • Ortiz de Montellano, Paul R.; Stearns, Ralph A.
  • Journal of the American Chemical Society, Vol. 109, Issue 11
  • DOI: 10.1021/ja00245a037

Fenton's reagent revisited
journal, April 1975


Electronic structures of active sites in copper proteins: contributions to reactivity
journal, June 1992

  • Solomon, Edward I.; Baldwin, Michael J.; Lowery, Michael D.
  • Chemical Reviews, Vol. 92, Issue 4
  • DOI: 10.1021/cr00012a003

Late-stage [ 18 F]fluorination: new solutions to old problems
journal, January 2014

  • Brooks, Allen F.; Topczewski, Joseph J.; Ichiishi, Naoko
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC02099E

LXXIII.—Oxidation of tartaric acid in presence of iron
journal, January 1894


Manganese Catalyzed C–H Halogenation
journal, May 2015


Metal-Free Fluorination of C(sp 3 )–H Bonds Using a Catalytic N -Oxyl Radical
journal, April 2013

  • Amaoka, Yuuki; Nagatomo, Masanori; Inoue, Masayuki
  • Organic Letters, Vol. 15, Issue 9
  • DOI: 10.1021/ol4006757

Versatility of biological non-heme Fe(II) centers in oxygen activation reactions
journal, February 2008

  • Kovaleva, Elena G.; Lipscomb, John D.
  • Nature Chemical Biology, Vol. 4, Issue 3
  • DOI: 10.1038/nchembio.71

Spectroscopic Evidence for the Two C–H-Cleaving Intermediates of Aspergillus nidulans Isopenicillin N Synthase
journal, July 2016

  • Tamanaha, Esta; Zhang, Bo; Guo, Yisong
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04065

Use of the cyclopropylcarbinyl test to detect a radical-like intermediate in penicillin biosynthesis
journal, January 1987

  • Baldwin, Jack E.; Adlington, Robert M.; Domayne-Hayman, Barbara P.
  • Journal of the Chemical Society, Chemical Communications, Issue 21
  • DOI: 10.1039/c39870001661

Time-Resolved Measurements of the Photolysis and Recombination of Adenosylcobalamin Bound to Glutamate Mutase
journal, September 2005

  • Sension, Roseanne J.; Harris, D. Ahmasi; Stickrath, Andrew
  • The Journal of Physical Chemistry B, Vol. 109, Issue 38
  • DOI: 10.1021/jp052492d

C-H bond activation in heme proteins: the role of thiolate ligation in cytochrome P450
journal, February 2009


A Common Late-Stage Intermediate in Catalysis by 2-Hydroxyethyl-phosphonate Dioxygenase and Methylphosphonate Synthase
journal, February 2015

  • Peck, Spencer C.; Chekan, Jonathan R.; Ulrich, Emily C.
  • Journal of the American Chemical Society, Vol. 137, Issue 9
  • DOI: 10.1021/jacs.5b00282

Oxidative Aliphatic C-H Fluorination with Fluoride Ion Catalyzed by a Manganese Porphyrin
journal, September 2012


Alkane activation and functionalization under mild conditions by a homogeneous manganese(III)porphyrin-iodosylbenzene oxidizing system
journal, September 1980

  • Hill, Craig L.; Schardt, Bruce C.
  • Journal of the American Chemical Society, Vol. 102, Issue 20
  • DOI: 10.1021/ja00540a049

Aqueous Ferryl(IV) Ion:  Kinetics of Oxygen Atom Transfer To Substrates and Oxo Exchange with Solvent Water
journal, January 2006

  • Pestovsky, Oleg; Bakac, Andreja
  • Inorganic Chemistry, Vol. 45, Issue 2
  • DOI: 10.1021/ic051868z

Electron photodetachment from mercaptyl anions (RS-). Electron affinities of mercaptyl radicals and the sulfur-hydrogen bond strength in mercaptans
journal, April 1980

  • Janousek, Bruce K.; Reed, Kenneth J.; Brauman, John I.
  • Journal of the American Chemical Society, Vol. 102, Issue 9
  • DOI: 10.1021/ja00529a040

Substrate activation for O2 reactions by oxidized metal centers in biology
journal, November 2007

  • Pau, M. Y. M.; Lipscomb, J. D.; Solomon, E. I.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 47
  • DOI: 10.1073/pnas.0704191104

Laboratory evolution of a soluble, self-sufficient, highly active alkane hydroxylase
journal, October 2002

  • Glieder, Anton; Farinas, Edgardo T.; Arnold, Frances H.
  • Nature Biotechnology, Vol. 20, Issue 11
  • DOI: 10.1038/nbt744

Aliphatic hydroxylation by highly purified liver microsomal cytochrome P-450. Evidence for a carbon radical intermediate
journal, March 1978

  • Groves, John T.; McClusky, Gary A.; White, Ronald E.
  • Biochemical and Biophysical Research Communications, Vol. 81, Issue 1
  • DOI: 10.1016/0006-291X(78)91643-1

Manganese Catalysts for C−H Activation: An Experimental/Theoretical Study Identifies the Stereoelectronic Factor That Controls the Switch between Hydroxylation and Desaturation Pathways
journal, June 2010

  • Hull, Jonathan F.; Balcells, David; Sauer, Effiette L. O.
  • Journal of the American Chemical Society, Vol. 132, Issue 22
  • DOI: 10.1021/ja908744w

Structural Analysis of an Open Active Site Conformation of Nonheme Iron Halogenase CytC3
journal, April 2009

  • Wong, Cintyu; Fujimori, Danica Galonić; Walsh, Christopher T.
  • Journal of the American Chemical Society, Vol. 131, Issue 13
  • DOI: 10.1021/ja8097355

Molecular probes of the mechanism of cytochrome P450. Oxygen traps a substrate radical intermediate
journal, March 2011

  • Cooper, Harriet L. R.; Groves, John T.
  • Archives of Biochemistry and Biophysics, Vol. 507, Issue 1
  • DOI: 10.1016/j.abb.2010.11.001

Fluorine Transfer to Alkyl Radicals
journal, February 2012

  • Rueda-Becerril, Montserrat; Chatalova Sazepin, Claire; Leung, Joe C. T.
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja211679v

The biology and chemistry of high-valent iron–oxo and iron–nitrido complexes
journal, January 2012

  • Hohenberger, Johannes; Ray, Kallol; Meyer, Karsten
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1718

Detection and Kinetic Characterization of a Highly Reactive Heme–Thiolate Peroxygenase Compound I
journal, July 2012

  • Wang, Xiaoshi; Peter, Sebastian; Kinne, Matthias
  • Journal of the American Chemical Society, Vol. 134, Issue 31
  • DOI: 10.1021/ja3049223

Structural Basis of Regiospecificity of a Mononuclear Iron Enzyme in Antibiotic Fosfomycin Biosynthesis
journal, July 2011

  • Yun, Danny; Dey, Mishtu; Higgins, Luke J.
  • Journal of the American Chemical Society, Vol. 133, Issue 29
  • DOI: 10.1021/ja2025728

A new family of iron-dependent halogenases acts on freestanding substrates
journal, September 2014


Structure of the key species in the enzymatic oxidation of methane to methanol
journal, January 2015

  • Banerjee, Rahul; Proshlyakov, Yegor; Lipscomb, John D.
  • Nature, Vol. 518, Issue 7539
  • DOI: 10.1038/nature14160

Isopenicillin N synthase: mechanistic studies
journal, November 1990


Parallel and Competitive Pathways for Substrate Desaturation, Hydroxylation, and Radical Rearrangement by the Non-heme Diiron Hydroxylase AlkB
journal, December 2012

  • Cooper, Harriet L. R.; Mishra, Girish; Huang, Xiongyi
  • Journal of the American Chemical Society, Vol. 134, Issue 50
  • DOI: 10.1021/ja3059149

Revisiting the Mechanism of P450 Enzymes with the Radical Clocks Norcarane and Spiro[2,5]octane
journal, May 2002

  • Auclair, Karine; Hu, Zhengbo; Little, Dorothy M.
  • Journal of the American Chemical Society, Vol. 124, Issue 21
  • DOI: 10.1021/ja025608h

Exploring substrate scope and stereoselectivity of P450 peroxygenase OleT JE in olefin-forming oxidative decarboxylation
journal, January 2016

  • Wang, Jian-bo; Lonsdale, Richard; Reetz, Manfred T.
  • Chemical Communications, Vol. 52, Issue 52
  • DOI: 10.1039/C6CC04345C

Oxygen Reactivity in Flavoenzymes: Context Matters
journal, October 2011

  • McDonald, Claudia A.; Fagan, Rebecca L.; Collard, François
  • Journal of the American Chemical Society, Vol. 133, Issue 42
  • DOI: 10.1021/ja2081873

From The Cover: SyrB2 in syringomycin E biosynthesis is a nonheme FeII  -ketoglutarate- and O2-dependent halogenase
journal, July 2005

  • Vaillancourt, F. H.; Yin, J.; Walsh, C. T.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 29
  • DOI: 10.1073/pnas.0504412102

Elucidation of the Fe(iv)=O intermediate in the catalytic cycle of the halogenase SyrB2
journal, July 2013

  • Wong, Shaun D.; Srnec, Martin; Matthews, Megan L.
  • Nature, Vol. 499, Issue 7458
  • DOI: 10.1038/nature12304

Understanding Hydrogen Atom Transfer: From Bond Strengths to Marcus Theory
journal, January 2011

  • Mayer, James M.
  • Accounts of Chemical Research, Vol. 44, Issue 1
  • DOI: 10.1021/ar100093z

Origin of the Regioselective Fatty-Acid Hydroxylation versus Decarboxylation by a Cytochrome P450 Peroxygenase: What Drives the Reaction to Biofuel Production?
journal, March 2016

  • Faponle, Abayomi S.; Quesne, Matthew G.; de Visser, Sam P.
  • Chemistry - A European Journal, Vol. 22, Issue 16
  • DOI: 10.1002/chem.201600739

Transition States in a Protein Environment − ONIOM QM:MM Modeling of Isopenicillin N Synthesis
journal, December 2008

  • Lundberg, Marcus; Kawatsu, Tsutomu; Vreven, Thom
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 1
  • DOI: 10.1021/ct800457g

Selective Monooxidation of Light Alkanes Using Chloride and Iodate
journal, May 2014

  • Fortman, George C.; Boaz, Nicholas C.; Munz, Dominik
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja502657g

X-ray Crystal Structure of Escherichia coli Taurine/α-Ketoglutarate Dioxygenase Complexed to Ferrous Iron and Substrates ,
journal, April 2002

  • Elkins, Jonathan M.; Ryle, Matthew J.; Clifton, Ian J.
  • Biochemistry, Vol. 41, Issue 16
  • DOI: 10.1021/bi016014e

Ferryl Protonation in Oxoiron(IV) Porphyrins and Its Role in Oxygen Transfer
journal, February 2015

  • Boaz, Nicholas C.; Bell, Seth R.; Groves, John T.
  • Journal of the American Chemical Society, Vol. 137, Issue 8
  • DOI: 10.1021/ja508759t

Equilibrium acidities in dimethyl sulfoxide solution
journal, December 1988

  • Bordwell, Frederick G.
  • Accounts of Chemical Research, Vol. 21, Issue 12
  • DOI: 10.1021/ar00156a004

Understanding organofluorine chemistry. An introduction to the C–F bond
journal, January 2008


Organic Azides: An Exploding Diversity of a Unique Class of Compounds
journal, August 2005

  • Bräse, Stefan; Gil, Carmen; Knepper, Kerstin
  • Angewandte Chemie International Edition, Vol. 44, Issue 33
  • DOI: 10.1002/anie.200400657

Merging Visible-Light Photocatalysis and Transition-Metal Catalysis in the Copper-Catalyzed Trifluoromethylation of Boronic Acids with CF 3 I
journal, May 2012

  • Ye, Yingda; Sanford, Melanie S.
  • Journal of the American Chemical Society, Vol. 134, Issue 22
  • DOI: 10.1021/ja301553c

Structural insight into antibiotic fosfomycin biosynthesis by a mononuclear iron enzyme
journal, July 2005

  • Higgins, Luke J.; Yan, Feng; Liu, Pinghua
  • Nature, Vol. 437, Issue 7060
  • DOI: 10.1038/nature03924

Does the Oxidation of Nitric Oxide by oxyMyoglobin Share an Intermediate with the metMyoglobin-Catalyzed Isomerization of Peroxynitrite?
journal, June 2013

  • Koebke, Karl J.; Pauly, Daniel J.; Lerner, Leonid
  • Inorganic Chemistry, Vol. 52, Issue 13
  • DOI: 10.1021/ic400697a

Manganese Porphyrins Catalyze Selective C−H Bond Halogenations
journal, September 2010

  • Liu, Wei; Groves, John T.
  • Journal of the American Chemical Society, Vol. 132, Issue 37
  • DOI: 10.1021/ja105548x

Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts
journal, January 2011

  • Che, Chi-Ming; Lo, Vanessa Kar-Yan; Zhou, Cong-Ying
  • Chemical Society Reviews, Vol. 40, Issue 4
  • DOI: 10.1039/c0cs00142b

Rhodium-Catalyzed C−C Bond Formation via Heteroatom-Directed C−H Bond Activation
journal, February 2010

  • Colby, Denise A.; Bergman, Robert G.; Ellman, Jonathan A.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr900005n

Mechanistic Investigation of Methylphosphonate Synthase, a Non-Heme Iron-Dependent Oxygenase
journal, September 2012

  • Cooke, Heather A.; Peck, Spencer C.; Evans, Bradley S.
  • Journal of the American Chemical Society, Vol. 134, Issue 38
  • DOI: 10.1021/ja306777w

511. The oxidation of aromatic compounds by means of the free hydroxyl radical
journal, January 1949


Expanding the substrate scope and reactivity of cytochrome P450 OleT
journal, August 2016

  • Hsieh, Chun H.; Makris, Thomas M.
  • Biochemical and Biophysical Research Communications, Vol. 476, Issue 4
  • DOI: 10.1016/j.bbrc.2016.05.145

Reactivity of Dioxygen−Copper Systems
journal, February 2004

  • Lewis, Elizabeth A.; Tolman, William B.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020633r

Direct, Catalytic Monofluorination of sp 3 C–H Bonds: A Radical-Based Mechanism with Ionic Selectivity
journal, June 2014

  • Pitts, Cody Ross; Bloom, Steven; Woltornist, Ryan
  • Journal of the American Chemical Society, Vol. 136, Issue 27
  • DOI: 10.1021/ja505136j

Photoredox Catalysis Unlocks Single-Electron Elementary Steps in Transition Metal Catalyzed Cross-Coupling
journal, May 2016


A transient intermediate of the methane monooxygenase catalytic cycle containing an FeIVFeIV cluster
journal, July 1993

  • Lee, Sang Kyu; Fox, Brian G.; Froland, Wayne A.
  • Journal of the American Chemical Society, Vol. 115, Issue 14
  • DOI: 10.1021/ja00067a086

A radical clock investigation of microsomal cytochrome P-450 hydroxylation of hydrocarbons. Rate of oxygen rebound
journal, July 1991

  • Bowry, Vincent W.; Ingold, K. U.
  • Journal of the American Chemical Society, Vol. 113, Issue 15
  • DOI: 10.1021/ja00015a025

Rapid Reduction of the Diferric-Peroxyhemiacetal Intermediate in Aldehyde-Deformylating Oxygenase by a Cyanobacterial Ferredoxin: Evidence for a Free-Radical Mechanism
journal, September 2015

  • Rajakovich, Lauren J.; Nørgaard, Hanne; Warui, Douglas M.
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b06345

Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides
journal, January 2015

  • Noble, Adam; McCarver, Stefan J.; MacMillan, David W. C.
  • Journal of the American Chemical Society, Vol. 137, Issue 2
  • DOI: 10.1021/ja511913h

Mechanistic insights into C–H activation from radical clock chemistry: oxidation of substituted methylcyclopropanes catalyzed by soluble methane monooxygenase from Methylosinus trichosporium OB3b
journal, November 2000

  • Jin, Yi; Lipscomb, John D.
  • Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology, Vol. 1543, Issue 1
  • DOI: 10.1016/S0167-4838(00)00199-0

Catalysis for fluorination and trifluoromethylation
journal, May 2011

  • Furuya, Takeru; Kamlet, Adam S.; Ritter, Tobias
  • Nature, Vol. 473, Issue 7348
  • DOI: 10.1038/nature10108

Substrate Placement Influences Reactivity in Non-heme Fe(II) Halogenases and Hydroxylases
journal, February 2013

  • Kulik, Heather J.; Drennan, Catherine L.
  • Journal of Biological Chemistry, Vol. 288, Issue 16
  • DOI: 10.1074/jbc.M112.415570

The Use of Heavy Oxygen in the Study of Reactions of Hydrogen Peroxide 1
journal, May 1952

  • Cahill, Allen E.; Taube, Henry
  • Journal of the American Chemical Society, Vol. 74, Issue 9
  • DOI: 10.1021/ja01129a042

Spectrum of chloroperoxidase compound I
journal, June 1980

  • Palcic, Monica M.; Rutter, Rick; Araiso, Tsunehisa
  • Biochemical and Biophysical Research Communications, Vol. 94, Issue 4
  • DOI: 10.1016/0006-291X(80)90535-5

The Non-Heme Diiron Alkane Monooxygenase of Pseudomonas o leovorans (AlkB) Hydroxylates via a Substrate Radical Intermediate
journal, November 2000

  • Austin, Rachel N.; Chang, Hung-Kuang; Zylstra, Gerben J.
  • Journal of the American Chemical Society, Vol. 122, Issue 47
  • DOI: 10.1021/ja001500v

Free-radical clocks
journal, September 1980

  • Griller, David; Ingold, Keith U.
  • Accounts of Chemical Research, Vol. 13, Issue 9
  • DOI: 10.1021/ar50153a004

Structural basis for halogenation by iron- and 2-oxo-glutarate-dependent enzyme WelO5
journal, June 2016

  • Mitchell, Andrew J.; Zhu, Qin; Maggiolo, Ailiena O.
  • Nature Chemical Biology, Vol. 12, Issue 8
  • DOI: 10.1038/nchembio.2112

Two-state reactivity mechanisms of hydroxylation and epoxidation by cytochrome P-450 revealed by theory
journal, October 2002

  • Shaik, Sason; de Visser, Samuël P.; Ogliaro, François
  • Current Opinion in Chemical Biology, Vol. 6, Issue 5
  • DOI: 10.1016/S1367-5931(02)00363-0

Transition metal catalysis and nucleophilic fluorination
journal, January 2012

  • Hollingworth, Charlotte; Gouverneur, Véronique
  • Chemical Communications, Vol. 48, Issue 24
  • DOI: 10.1039/c2cc16158c

The bioinorganic chemistry of iron in oxygenases and supramolecular assemblies
journal, March 2003

  • Groves, J. T.
  • Proceedings of the National Academy of Sciences, Vol. 100, Issue 7, p. 3569-3574
  • DOI: 10.1073/pnas.0830019100

Protein Free Energy Corrections in ONIOM QM:MM Modeling: A Case Study for Isopenicillin N Synthase (IPNS)
journal, December 2010

  • Kawatsu, Tsutomu; Lundberg, Marcus; Morokuma, Keiji
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 2
  • DOI: 10.1021/ct1005592

Ferryl ion, a Compound of Tetravalent iron
journal, May 1932

  • Bray, William C.; Gorin, M. H.
  • Journal of the American Chemical Society, Vol. 54, Issue 5
  • DOI: 10.1021/ja01344a505

Evidence for an Alternative to the Oxygen Rebound Mechanism in C–H Bond Activation by Non-Heme Fe IV O Complexes
journal, December 2012

  • Cho, Kyung-Bin; Wu, Xiujuan; Lee, Yong-Min
  • Journal of the American Chemical Society, Vol. 134, Issue 50
  • DOI: 10.1021/ja308290r

Synthesis of 11 C, 18 F, 15 O, and 13 N Radiolabels for Positron Emission Tomography
journal, November 2008

  • Miller, Philip W.; Long, Nicholas J.; Vilar, Ramon
  • Angewandte Chemie International Edition, Vol. 47, Issue 47
  • DOI: 10.1002/anie.200800222

Protein Radicals in Enzyme Catalysis
journal, April 1998

  • Stubbe, JoAnne; van der Donk, Wilfred A.
  • Chemical Reviews, Vol. 98, Issue 2
  • DOI: 10.1021/cr9400875

Catalytic strategy for carbon−carbon bond scission by the cytochrome P450 OleT
journal, August 2016

  • Grant, Job L.; Mitchell, Megan E.; Makris, Thomas Michael
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 36
  • DOI: 10.1073/pnas.1606294113

Electron-nuclear double resonance spectroscopy (and electron spin-echo envelope modulation spectroscopy) in bioinorganic chemistry
journal, March 2003


Mechanistic Studies on the Hydroxylation of Methane by Methane Monooxygenase
journal, June 2003

  • Baik, Mu-Hyun; Newcomb, Martin; Friesner, Richard A.
  • Chemical Reviews, Vol. 103, Issue 6
  • DOI: 10.1021/cr950244f

Hydroxylation by the Hydroperoxy-Iron Species in Cytochrome P450 Enzymes
journal, January 2004

  • Chandrasena, R. Esala P.; Vatsis, Kostas P.; Coon, Minor J.
  • Journal of the American Chemical Society, Vol. 126, Issue 1
  • DOI: 10.1021/ja038237t

Visible Light-Promoted Metal-Free C–H Activation: Diarylketone-Catalyzed Selective Benzylic Mono- and Difluorination
journal, November 2013

  • Xia, Ji-Bao; Zhu, Chen; Chen, Chuo
  • Journal of the American Chemical Society, Vol. 135, Issue 46
  • DOI: 10.1021/ja410815u

Palladium-Catalyzed Ligand-Directed C−H Functionalization Reactions
journal, February 2010

  • Lyons, Thomas W.; Sanford, Melanie S.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr900184e

A Model “Rebound” Mechanism of Hydroxylation by Cytochrome P450:  Stepwise and Effectively Concerted Pathways, and Their Reactivity Patterns
journal, September 2000

  • Ogliaro, François; Harris, Nathan; Cohen, Shimrit
  • Journal of the American Chemical Society, Vol. 122, Issue 37
  • DOI: 10.1021/ja991878x

Mechanisms of Organic Oxidation and Reduction by Metal Complexes
journal, January 1967


I. Ligand transfer of halides (chloride, bromide, iodide) and pseudohalides (thiocyanate, azide, cyanide) from copper(II) to alkyl radicals
journal, October 1971

  • Kochi, J. K.; Jenkins, C. L.
  • The Journal of Organic Chemistry, Vol. 36, Issue 21
  • DOI: 10.1021/jo00820a008

Transition-Metal Hydride Radical Cations
journal, February 2016


Iron-Catalyzed Halogenation of Alkanes: Modeling of Nonheme Halogenases by Experiment and DFT Calculations
journal, May 2010

  • Comba, Peter; Wunderlich, Steffen
  • Chemistry - A European Journal, Vol. 16, Issue 24
  • DOI: 10.1002/chem.201000092

Compounds I of Catalase and Horse Radish Peroxidase:  -Cation Radicals
journal, March 1971

  • Dolphin, D.; Forman, A.; Borg, D. C.
  • Proceedings of the National Academy of Sciences, Vol. 68, Issue 3
  • DOI: 10.1073/pnas.68.3.614

Synthesis of Methylphosphonic Acid by Marine Microbes: A Source for Methane in the Aerobic Ocean
journal, August 2012


Substrate-Induced Conformational Changes in Escherichia coli Taurine/α-Ketoglutarate Dioxygenase and Insight into the Oligomeric Structure
journal, May 2003

  • O'Brien, Jessica R.; Schuller, David J.; Yang, Victoria S.
  • Biochemistry, Vol. 42, Issue 19
  • DOI: 10.1021/bi0341096

Understanding and exploiting C–H bond activation
journal, May 2002

  • Labinger, Jay A.; Bercaw, John E.
  • Nature, Vol. 417, Issue 6888
  • DOI: 10.1038/417507a

Stereospecific aliphatic hydroxylation by iron-hydrogen peroxide. Evidence for a stepwise process
journal, August 1976

  • Groves, John T.; Van der Puy, Michael
  • Journal of the American Chemical Society, Vol. 98, Issue 17
  • DOI: 10.1021/ja00433a039

Radicals: Reactive Intermediates with Translational Potential
journal, September 2016

  • Yan, Ming; Lo, Julian C.; Edwards, Jacob T.
  • Journal of the American Chemical Society, Vol. 138, Issue 39
  • DOI: 10.1021/jacs.6b08856

Merging photoredox with nickel catalysis: Coupling of  -carboxyl sp3-carbons with aryl halides
journal, June 2014


Structure and Spectroscopy of Copper−Dioxygen Complexes
journal, February 2004

  • Mirica, Liviu M.; Ottenwaelder, Xavier; Stack, T. Daniel P.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020632z

Metal-catalysed azidation of tertiary C–H bonds suitable for late-stage functionalization
journal, January 2015


Iron Catalysis in Organic Synthesis
journal, March 2015

  • Bauer, Ingmar; Knölker, Hans-Joachim
  • Chemical Reviews, Vol. 115, Issue 9
  • DOI: 10.1021/cr500425u

The Cytochrome P450-Catalyzed Oxidative Rearrangement in the Final Step of Pentalenolactone Biosynthesis: Substrate Structure Determines Mechanism
journal, September 2016

  • Duan, Lian; Jogl, Gerwald; Cane, David E.
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b08610

Targeted Fluorination with the Fluoride Ion by Manganese-Catalyzed Decarboxylation
journal, March 2015

  • Huang, Xiongyi; Liu, Wei; Hooker, Jacob M.
  • Angewandte Chemie International Edition, Vol. 54, Issue 17
  • DOI: 10.1002/anie.201500399

Click Chemistry for Drug Development and Diverse Chemical–Biology Applications
journal, March 2013

  • Thirumurugan, Prakasam; Matosiuk, Dariusz; Jozwiak, Krzysztof
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr200409f

Trans-dioxo Manganese(V) Porphyrins
journal, October 2007

  • Jin, Ning; Ibrahim, Mohammed; Spiro, Thomas G.
  • Journal of the American Chemical Society, Vol. 129, Issue 41
  • DOI: 10.1021/ja0761737

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
journal, March 2013

  • Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr300503r

Biologically inspired oxidation catalysis
journal, September 2008


Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450
journal, November 2013


First-Principles Study of Non-heme Fe(II) Halogenase SyrB2 Reactivity
journal, October 2009

  • Kulik, Heather J.; Blasiak, Leah C.; Marzari, Nicola
  • Journal of the American Chemical Society, Vol. 131, Issue 40
  • DOI: 10.1021/ja905206k

Chemistry of singlet oxygen. 51. Zwitterionic intermediates from 2,4-hexadienes
journal, October 1988

  • O'Shea, Kevin E.; Foote, Christopher S.
  • Journal of the American Chemical Society, Vol. 110, Issue 21
  • DOI: 10.1021/ja00229a035

Crystal structure of the non-haem iron halogenase SyrB2 in syringomycin biosynthesis
journal, March 2006

  • Blasiak, Leah C.; Vaillancourt, Frédéric H.; Walsh, Christopher T.
  • Nature, Vol. 440, Issue 7082
  • DOI: 10.1038/nature04544

Alkane functionalization at nonheme iron centers. Stoichiometric transfer of metal-bound ligands to alkane
journal, December 1993

  • Kojima, Takahiko; Leising, Randolph A.; Yan, Shiping
  • Journal of the American Chemical Society, Vol. 115, Issue 24
  • DOI: 10.1021/ja00077a035

First Crystal Structure of a Fungal High-redox Potential Dye-decolorizing Peroxidase: SUBSTRATE INTERACTION SITES AND LONG-RANGE ELECTRON TRANSFER
journal, December 2012

  • Strittmatter, Eric; Liers, Christiane; Ullrich, René
  • Journal of Biological Chemistry, Vol. 288, Issue 6
  • DOI: 10.1074/jbc.M112.400176

On the status of ferryl protonation
journal, April 2006


Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis
journal, June 2014


Iron(II) Catalysis in Oxidation of Hydrocarbons with Ozone in Acetonitrile
journal, February 2015

  • Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501962m

Aryl amination using ligand-free Ni(II) salts and photoredox catalysis
journal, June 2016


Terminal Olefin (1-Alkene) Biosynthesis by a Novel P450 Fatty Acid Decarboxylase from Jeotgalicoccus Species
journal, January 2011

  • Rude, Mathew A.; Baron, Tarah S.; Brubaker, Shane
  • Applied and Environmental Microbiology, Vol. 77, Issue 5
  • DOI: 10.1128/AEM.02580-10

Aliphatic hydroxylation via oxygen rebound. Oxygen transfer catalyzed by iron
journal, February 1976

  • Groves, John T.; McClusky, Gary A.
  • Journal of the American Chemical Society, Vol. 98, Issue 3
  • DOI: 10.1021/ja00419a049

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010

  • Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
  • Chemical Reviews, Vol. 110, Issue 12
  • DOI: 10.1021/cr100085k

The Formation of Iron(IV) in the Oxidation of Iron(II) 1
journal, February 1965

  • Conocchioli, T. J.; Hamilton, E. J.; Sutin, N.
  • Journal of the American Chemical Society, Vol. 87, Issue 4
  • DOI: 10.1021/ja01082a050

To rebound or dissociate? This is the mechanistic question in C–H hydroxylation by heme and nonheme metal–oxo complexes
journal, January 2016

  • Cho, Kyung-Bin; Hirao, Hajime; Shaik, Sason
  • Chemical Society Reviews, Vol. 45, Issue 5
  • DOI: 10.1039/C5CS00566C

Hydrocarbon Hydroxylation by Cytochrome P450 Enzymes
journal, February 2010

  • Ortiz de Montellano, Paul R.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr9002193

Key elements of the chemistry of cytochrome P-450: The oxygen rebound mechanism
journal, November 1985

  • Groves, John T.
  • Journal of Chemical Education, Vol. 62, Issue 11
  • DOI: 10.1021/ed062p928

Dioxygen Activation by Enzymes Containing Binuclear Non-Heme Iron Clusters
journal, January 1996

  • Wallar, Bradley J.; Lipscomb, John D.
  • Chemical Reviews, Vol. 96, Issue 7
  • DOI: 10.1021/cr9500489

The enigmatic reaction of flavins with oxygen
journal, September 2012

  • Chaiyen, Pimchai; Fraaije, Marco W.; Mattevi, Andrea
  • Trends in Biochemical Sciences, Vol. 37, Issue 9
  • DOI: 10.1016/j.tibs.2012.06.005

Direct Detection of the Oxygen Rebound Intermediates, Ferryl Mb and NO 2 , in the Reaction of metMyoglobin with Peroxynitrite
journal, September 2009

  • Su, Jia; Groves, John T.
  • Journal of the American Chemical Society, Vol. 131, Issue 36
  • DOI: 10.1021/ja902473r

Multicopper Oxidases and Oxygenases
journal, January 1996

  • Solomon, Edward I.; Sundaram, Uma M.; Machonkin, Timothy E.
  • Chemical Reviews, Vol. 96, Issue 7
  • DOI: 10.1021/cr950046o

Evidence that the Fosfomycin-Producing Epoxidase, HppE, Is a Non-Heme-Iron Peroxidase
journal, October 2013


Enzymatic functionalization of carbon–hydrogen bonds
journal, January 2011

  • Lewis, Jared C.; Coelho, Pedro S.; Arnold, Frances H.
  • Chem. Soc. Rev., Vol. 40, Issue 4
  • DOI: 10.1039/C0CS00067A

Kinetic Isotope Effects Implicate Two Electrophilic Oxidants in Cytochrome P450-Catalyzed Hydroxylations
journal, May 2003

  • Newcomb, Martin; Aebisher, David; Shen, Runnan
  • Journal of the American Chemical Society, Vol. 125, Issue 20
  • DOI: 10.1021/ja0343858

Experimental Correlation of Substrate Position with Reaction Outcome in the Aliphatic Halogenase, SyrB2
journal, May 2015

  • Martinie, Ryan J.; Livada, Jovan; Chang, Wei-chen
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b03370

Cage Escape Competes with Geminate Recombination during Alkane Hydroxylation by the Diiron Oxygenase AlkB
journal, June 2008

  • Austin, Rachel N.; Luddy, Kate; Erickson, Karla
  • Angewandte Chemie International Edition, Vol. 47, Issue 28
  • DOI: 10.1002/anie.200801184

Asymmetric copper-catalyzed C-N cross-couplings induced by visible light
journal, February 2016


Nickel-Catalyzed Cross-Coupling of Redox-Active Esters with Boronic Acids
journal, July 2016

  • Wang, Jie; Qin, Tian; Chen, Tie-Gen
  • Angewandte Chemie International Edition, Vol. 55, Issue 33
  • DOI: 10.1002/anie.201605463

Electron-transfer mechanisms for organometallic intermediates in catalytic reactions
journal, October 1974


Mechanisms of Peroxynitrite Interactions with Heme Proteins
journal, July 2010

  • Su, Jia; Groves, John T.
  • Inorganic Chemistry, Vol. 49, Issue 14
  • DOI: 10.1021/ic902157z

Correlating DFT-Calculated Energy Barriers to Experiments in Nonheme Octahedral FeIVO Species
journal, June 2012

  • Cho, Kyung-Bin; Kim, Eun Jeong; Seo, Mi Sook
  • Chemistry - A European Journal, Vol. 18, Issue 33
  • DOI: 10.1002/chem.201200096

Substrate-Triggered Formation and Remarkable Stability of the C−H Bond-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2
journal, May 2009

  • Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.
  • Biochemistry, Vol. 48, Issue 20
  • DOI: 10.1021/bi900109z

Theoretical Investigations into C–H Bond Activation Reaction by Nonheme Mn IV O Complexes: Multistate Reactivity with No Oxygen Rebound
journal, September 2012

  • Cho, Kyung-Bin; Shaik, Sason; Nam, Wonwoo
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 19
  • DOI: 10.1021/jz301241z

Evolution of C–H Bond Functionalization from Methane to Methodology
journal, December 2015

  • Hartwig, John F.
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b08707

Time-Resolved Spectroscopic Studies of B 12 Coenzymes:  Influence of Solvent on the Photolysis of Adenosylcobalamin
journal, December 2001

  • Yoder, Laurie M.; Cole, Allwyn G.; Walker, Larry A.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 48
  • DOI: 10.1021/jp012157z

Late Stage Benzylic C–H Fluorination with [ 18 F]Fluoride for PET Imaging
journal, May 2014

  • Huang, Xiongyi; Liu, Wei; Ren, Hong
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja5039819

Taming Azide Radicals for Catalytic C–H Azidation
journal, December 2015


Xylene monooxygenase, a membrane-spanning non-heme diiron enzyme that hydroxylates hydrocarbons via a substrate radical intermediate
journal, June 2003

  • Austin, Rachel N.; Buzzi, Kate; Kim, Eungbin
  • JBIC Journal of Biological Inorganic Chemistry, Vol. 8, Issue 7
  • DOI: 10.1007/s00775-003-0466-3

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    • DOI: 10.1002/hlca.201800044

    Manganese-salen catalyzed oxidative benzylic chlorination
    journal, July 2018

    • Sasmal, Sheuli; Rana, Sujoy; Lahiri, Goutam Kumar
    • Journal of Chemical Sciences, Vol. 130, Issue 7
    • DOI: 10.1007/s12039-018-1511-7

    Recent examples of α-ketoglutarate-dependent mononuclear non-haem iron enzymes in natural product biosyntheses
    journal, January 2018

    • Gao, Shu-Shan; Naowarojna, Nathchar; Cheng, Ronghai
    • Natural Product Reports, Vol. 35, Issue 8
    • DOI: 10.1039/c7np00067g

    Enhancing microperoxidase activity and selectivity: immobilization in metal-organic frameworks
    journal, July 2019

    • Gkaniatsou, Effrosyni; Serre, Christian; Mahy, Jean-Pierre
    • Journal of Porphyrins and Phthalocyanines, Vol. 23, Issue 07n08
    • DOI: 10.1142/s1088424619300106

    Electrochemistry and Photoredox Catalysis: A Comparative Evaluation in Organic Synthesis
    journal, June 2019


    Site- and Enantioselective C−H Oxygenation Catalyzed by a Chiral Manganese Porphyrin Complex with a Remote Binding Site
    journal, February 2018

    • Burg, Finn; Gicquel, Maxime; Breitenlechner, Stefan
    • Angewandte Chemie International Edition, Vol. 57, Issue 11
    • DOI: 10.1002/anie.201712340

    Design of A Metabolically Stable Tritium-Tracer of the PI3K δ -Inhibitor CDZ173 (Leniolisib) as a Tool to Study Liver Metabolites
    journal, June 2018

    • Bauer, Carsten; Luu, Tong; Eggimann, Fabian
    • Helvetica Chimica Acta, Vol. 101, Issue 6
    • DOI: 10.1002/hlca.201800044

    Manganese-salen catalyzed oxidative benzylic chlorination
    journal, July 2018

    • Sasmal, Sheuli; Rana, Sujoy; Lahiri, Goutam Kumar
    • Journal of Chemical Sciences, Vol. 130, Issue 7
    • DOI: 10.1007/s12039-018-1511-7

    Recent examples of α-ketoglutarate-dependent mononuclear non-haem iron enzymes in natural product biosyntheses
    journal, January 2018

    • Gao, Shu-Shan; Naowarojna, Nathchar; Cheng, Ronghai
    • Natural Product Reports, Vol. 35, Issue 8
    • DOI: 10.1039/c7np00067g

    Enhancing microperoxidase activity and selectivity: immobilization in metal-organic frameworks
    journal, July 2019

    • Gkaniatsou, Effrosyni; Serre, Christian; Mahy, Jean-Pierre
    • Journal of Porphyrins and Phthalocyanines, Vol. 23, Issue 07n08
    • DOI: 10.1142/s1088424619300106

    Electrochemistry and Photoredox Catalysis: A Comparative Evaluation in Organic Synthesis
    journal, June 2019