Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity

Nutting, Jordan E.; Mao, Kaining; Stahl, Shannon S.

doi:10.1021/jacs.1c05224

Title: Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity

Abstract

Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature “integrated cooperativity”, in which Cu^II and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for “serial cooperativity”, involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NO_x-based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. Here, the different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.

Authors:

^[1]; Mao, Kaining ^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)

Publication Date:: Wed Jul 07 00:00:00 EDT 2021

Research Org.:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Org.:: USDOE; National Science Foundation (NSF)

OSTI Identifier:: 1819738

Grant/Contract Number:: FG02-05ER15690; CHE-1048642

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 143; Journal Issue: 28; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; Alcohols; Cooperativity; Catalysts; Oxidation

Citation Formats


                    Nutting, Jordan E., Mao, Kaining, and Stahl, Shannon S. Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity.  United States: N. p., 2021. 
Web.  doi:10.1021/jacs.1c05224.

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                    Nutting, Jordan E., Mao, Kaining, & Stahl, Shannon S. Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity.  United States.  https://doi.org/10.1021/jacs.1c05224

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                    Nutting, Jordan E., Mao, Kaining, and Stahl, Shannon S. Wed .  
"Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity".  United States.  https://doi.org/10.1021/jacs.1c05224.  https://www.osti.gov/servlets/purl/1819738.

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@article{osti_1819738,

  title        = {Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity},

  author       = {Nutting, Jordan E. and Mao, Kaining and Stahl, Shannon S.},

  abstractNote = {Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature “integrated cooperativity”, in which CuII and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for “serial cooperativity”, involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NOx-based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. Here, the different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.},

  doi          = {10.1021/jacs.1c05224},

  journal      = {Journal of the American Chemical Society},

  number       = 28,

  volume       = 143,

  place        = {United States},

  year         = {Wed Jul 07 00:00:00 EDT 2021},

  month        = {Wed Jul 07 00:00:00 EDT 2021}

}

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Works referenced in this record:

On the Use of Stable Organic Nitroxyl Radicals for the Oxidation of Primary and Secondary Alcohols
journal, October 1996

Nooy, Arjan E. J. de; Besemer, Arie C.; Bekkum, Herman van
Synthesis, Vol. 1996, Issue 10
DOI: 10.1055/s-1996-4369

Nitroxide-catalyzed transition-metal-free aerobic oxidation processes
journal, January 2013

Wertz, Sebastian; Studer, Armido
Green Chemistry, Vol. 15, Issue 11
DOI: 10.1039/c3gc41459k

Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Copper/TEMPO and Related Catalyst Systems
journal, July 2014

Ryland, Bradford L.; Stahl, Shannon S.
Angewandte Chemie International Edition, Vol. 53, Issue 34
DOI: 10.1002/anie.201403110

Aerobic oxidation catalysis with stable radicals
journal, January 2014

Cao, Qun; Dornan, Laura M.; Rogan, Luke
Chem. Commun., Vol. 50, Issue 35
DOI: 10.1039/C3CC47081D

Tetramethylpiperidine N -Oxyl (TEMPO), Phthalimide N -Oxyl (PINO), and Related N -Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions
journal, April 2018

Nutting, Jordan E.; Rafiee, Mohammad; Stahl, Shannon S.
Chemical Reviews, Vol. 118, Issue 9
DOI: 10.1021/acs.chemrev.7b00763

Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions
journal, June 1987

Lucio Anelli, Pier; Biffi, Carlo; Montanari, Fernando
The Journal of Organic Chemistry, Vol. 52, Issue 12
DOI: 10.1021/jo00388a038

Large-Scale Oxidations in the Pharmaceutical Industry ^†
journal, July 2006

Caron, Stéphane; Dugger, Robert W.; Ruggeri, Sally Gut
Chemical Reviews, Vol. 106, Issue 7
DOI: 10.1021/cr040679f

Cu(ii)-nitroxyl radicals as catalytic galactose oxidase mimics
journal, January 2003

Dijksman, Arn�; Arends, Isabel W. C. E.; Sheldon, Roger A.
Organic & Biomolecular Chemistry, Vol. 1, Issue 18
DOI: 10.1039/b305941c

Cu(bipy) ²⁺ /TEMPO-Catalyzed Oxidation of Alcohols: Radical or Nonradical Mechanism?
journal, December 2011

Belanzoni, Paola; Michel, Carine; Baerends, Evert Jan
Inorganic Chemistry, Vol. 50, Issue 23
DOI: 10.1021/ic200725k

Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation
journal, January 2013

Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.
Journal of the American Chemical Society, Vol. 135, Issue 6
DOI: 10.1021/ja3117203

Mechanism of Alcohol Oxidation Mediated by Copper(II) and Nitroxyl Radicals
journal, August 2014

Ryland, Bradford L.; McCann, Scott D.; Brunold, Thomas C.
Journal of the American Chemical Society, Vol. 136, Issue 34
DOI: 10.1021/ja5070137

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators
journal, June 2016

Badalyan, Artavazd; Stahl, Shannon S.
Nature, Vol. 535, Issue 7612
DOI: 10.1038/nature18008

Reaction of Cyclic Nitroxides with Nitrogen Dioxide: The Intermediacy of the Oxoammonium Cations
journal, July 2003

Goldstein, Sara; Samuni, Amram; Russo, Angelo
Journal of the American Chemical Society, Vol. 125, Issue 27
DOI: 10.1021/ja035286x

High-Potential Electrocatalytic O ₂ Reduction with Nitroxyl/NO _x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis
journal, July 2015

Gerken, James B.; Stahl, Shannon S.
ACS Central Science, Vol. 1, Issue 5
DOI: 10.1021/acscentsci.5b00163

NaNO2-activated, iron–TEMPO catalyst system for aerobic alcohol oxidation under mild conditions
journal, January 2005

Wang, Naiwei; Liu, Renhua; Chen, Jiping
Chemical Communications, Issue 42
DOI: 10.1039/b509167e

Iron Chloride/4-Acetamido-TEMPO/Sodium Nitrite-Catalyzed Aerobic Oxidation of Primary Alcohols to the Aldehydes
journal, January 2010

Yin, Weili; Chu, Changhu; Lu, Qiongqiong
Advanced Synthesis & Catalysis, Vol. 352, Issue 1
DOI: 10.1002/adsc.200900662

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt
journal, April 2011

Ma, Shengming; Liu, Jinxian; Li, Suhua
Advanced Synthesis & Catalysis, Vol. 353, Issue 6, p. 1005-1017
DOI: 10.1002/adsc.201100033

Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids
journal, June 2016

Jiang, Xingguo; Zhang, Jiasheng; Ma, Shengming
Journal of the American Chemical Society, Vol. 138, Issue 27
DOI: 10.1021/jacs.6b03948

Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
journal, February 2016

Wang, Lianyue; Shang, SenSen; Li, Guosong
The Journal of Organic Chemistry, Vol. 81, Issue 5
DOI: 10.1021/acs.joc.6b00009

Iron-Catalyzed Aerobic Oxidation of Alcohols: Lower Cost and Improved Selectivity
journal, March 2019

Jiang, Xingguo; Liu, Jinxian; Ma, Shengming
Organic Process Research & Development, Vol. 23, Issue 5
DOI: 10.1021/acs.oprd.8b00374

Metal Nitrate Catalysis for Selective Oxidation of 5-Hydroxymethylfurfural into 2,5-Diformylfuran under Oxygen Atmosphere
journal, April 2019

Hong, Mei; Min, Jie; Wu, Shuangyan
ACS Omega, Vol. 4, Issue 4
DOI: 10.1021/acsomega.9b00391

Tuning the Reactivity of TEMPO by Coordination to a Lewis Acid: Isolation and Reactivity of MCl ₃ (η ¹ -TEMPO) (M = Fe, Al)
journal, November 2012

Scepaniak, Jeremiah J.; Wright, Ashley M.; Lewis, Richard A.
Journal of the American Chemical Society, Vol. 134, Issue 47
DOI: 10.1021/ja309499h

Oxidation of Alcohols and Activated Alkanes with Lewis Acid-Activated TEMPO
journal, October 2014

Nguyen, Thuy-Ai D.; Wright, Ashley M.; Page, Joshua S.
Inorganic Chemistry, Vol. 53, Issue 21
DOI: 10.1021/ic5018888

Kinetics of Nitroxide Reaction with Iron(II)
journal, September 1999

Bar-On, Pazit; Mohsen, Mohammad; Zhang, Renliang
Journal of the American Chemical Society, Vol. 121, Issue 35
DOI: 10.1021/ja990623g

Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects
journal, November 2015

Rafiee, Mohammad; Miles, Kelsey C.; Stahl, Shannon S.
Journal of the American Chemical Society, Vol. 137, Issue 46, p. 14751-14757
DOI: 10.1021/jacs.5b09672

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013

Rahimi, Alireza; Azarpira, Ali; Kim, Hoon
Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418
DOI: 10.1021/ja401793n

Electrochemical studies of acid-promoted disproportionation of nitroxyl radical
journal, May 2003

Kishioka, Shin-ya; Ohsaka, Takeo; Tokuda, Koichi
Electrochimica Acta, Vol. 48, Issue 11
DOI: 10.1016/S0013-4686(03)00024-0

Equilibrium Acidities of Superacids
journal, January 2011

Kütt, Agnes; Rodima, Toomas; Saame, Jaan
The Journal of Organic Chemistry, Vol. 76, Issue 2
DOI: 10.1021/jo101409p

Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs
journal, November 2017

Gerken, James B.; Pang, Yutong Q.; Lauber, Markus B.
The Journal of Organic Chemistry, Vol. 83, Issue 14
DOI: 10.1021/acs.joc.7b02547

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character
journal, September 2017

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.
Journal of the American Chemical Society, Vol. 139, Issue 38
DOI: 10.1021/jacs.7b07186

Divergent Reactivity of TEMPO with MBr ₃ (M = B, Al)
journal, April 2013

Wright, Ashley M.; Page, Joshua S.; Scepaniak, Jeremiah J.
European Journal of Inorganic Chemistry, Vol. 2013, Issue 22-23
DOI: 10.1002/ejic.201300163

A kinetics study of the oxidation of iron(II) by nitric acid
journal, May 1980

Epstein, Irving R.; Kustin, Kenneth; Warshaw, Linda Joyce
Journal of the American Chemical Society, Vol. 102, Issue 11
DOI: 10.1021/ja00531a015

Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols
journal, October 2011

Hoover, Jessica M.; Stahl, Shannon S.
Journal of the American Chemical Society, Vol. 133, Issue 42
DOI: 10.1021/ja206230h

Efficient Aerobic Oxidation of Secondary Alcohols at Ambient Temperature with an ABNO/NO _x Catalyst System
journal, October 2013

Lauber, Markus B.; Stahl, Shannon S.
ACS Catalysis, Vol. 3, Issue 11
DOI: 10.1021/cs400746m

Mechanism of oxidation of primary and secondary alcohols by oxopiperidinium salts
journal, September 1977

Golubev, V. A.; Borislavskii, V. N.; Aleksandrov, A. L.
Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 26, Issue 9
DOI: 10.1007/BF00924380

Mechanism of the Oxidation of Alcohols by Oxoammonium Cations
journal, June 2007

Bailey, William F.; Bobbitt, James M.; Wiberg, Kenneth B.
The Journal of Organic Chemistry, Vol. 72, Issue 12
DOI: 10.1021/jo0704614

Multichannel gas-uptake/evolution reactor for monitoring liquid-phase chemical reactions
journal, April 2021

Salazar, Chase A.; Thompson, Blaise J.; Knapp, Spring M. M.
Review of Scientific Instruments, Vol. 92, Issue 4
DOI: 10.1063/5.0043007

Catalytic Activity Dependency on Catalyst Components in Aerobic Copper-TEMPO Oxidation
journal, September 2009

Kumpulainen, Esa T. T.; Koskinen, Ari M. P.
Chemistry - A European Journal, Vol. 15, Issue 41
DOI: 10.1002/chem.200901245

Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds
journal, February 2014

Sasano, Yusuke; Nagasawa, Shota; Yamazaki, Mai
Angewandte Chemie International Edition, Vol. 53, Issue 12
DOI: 10.1002/anie.201309634

2-Azaadamantane N -oxyl (AZADO)/Cu Catalysis Enables Chemoselective Aerobic Oxidation of Alcohols Containing Electron-Rich Divalent Sulfur Functionalities
journal, September 2018

Sasano, Yusuke; Kogure, Naoki; Nagasawa, Shota
Organic Letters, Vol. 20, Issue 19
DOI: 10.1021/acs.orglett.8b02528

Copper catalysis for highly selective aerobic oxidation of alcohols to aldehydes/ketones
journal, January 2019

Zhai, Di; Ma, Shengming
Organic Chemistry Frontiers, Vol. 6, Issue 17
DOI: 10.1039/C9QO00740G

Iron-Catalysed Selective Aerobic Oxidation of Alcohols to Carbonyl and Carboxylic Compounds
journal, July 2016

Lagerblom, Kalle; Wrigstedt, Pauli; Keskiväli, Juha
ChemPlusChem, Vol. 81, Issue 11
DOI: 10.1002/cplu.201600240

Process Development of CuI/ABNO/NMI-Catalyzed Aerobic Alcohol Oxidation
journal, July 2015

Steves, Janelle E.; Preger, Yuliya; Martinelli, Joseph R.
Organic Process Research & Development, Vol. 19, Issue 11
DOI: 10.1021/acs.oprd.5b00179

Synthesis of HIV-Maturation Inhibitor BMS-955176 from Betulin by an Enabling Oxidation Strategy
journal, April 2017

Ortiz, Adrian; Soumeillant, Maxime; Savage, Scott A.
The Journal of Organic Chemistry, Vol. 82, Issue 9
DOI: 10.1021/acs.joc.7b00438

Development of a Large-Scale Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation for the Synthesis of LSD1 Inhibitor GSK2879552
journal, October 2018

Ochen, Augustine; Whitten, Robert; Aylott, Helen E.
Organometallics, Vol. 38, Issue 1
DOI: 10.1021/acs.organomet.8b00546

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Title: Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity

Abstract

Citation Formats

On the Use of Stable Organic Nitroxyl Radicals for the Oxidation of Primary and Secondary Alcohols journal, October 1996

Nitroxide-catalyzed transition-metal-free aerobic oxidation processes journal, January 2013

Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Copper/TEMPO and Related Catalyst Systems journal, July 2014

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Tetramethylpiperidine N -Oxyl (TEMPO), Phthalimide N -Oxyl (PINO), and Related N -Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions journal, April 2018

Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions journal, June 1987

Large-Scale Oxidations in the Pharmaceutical Industry † journal, July 2006

Cu(ii)-nitroxyl radicals as catalytic galactose oxidase mimics journal, January 2003

Cu(bipy) 2+ /TEMPO-Catalyzed Oxidation of Alcohols: Radical or Nonradical Mechanism? journal, December 2011

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Mechanism of Alcohol Oxidation Mediated by Copper(II) and Nitroxyl Radicals journal, August 2014

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Kinetics of Nitroxide Reaction with Iron(II) journal, September 1999

Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects journal, November 2015

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin journal, April 2013

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Equilibrium Acidities of Superacids journal, January 2011

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Divergent Reactivity of TEMPO with MBr 3 (M = B, Al) journal, April 2013

A kinetics study of the oxidation of iron(II) by nitric acid journal, May 1980

Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols journal, October 2011

Efficient Aerobic Oxidation of Secondary Alcohols at Ambient Temperature with an ABNO/NO x Catalyst System journal, October 2013

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On the Use of Stable Organic Nitroxyl Radicals for the Oxidation of Primary and Secondary Alcohols
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journal, August 2014

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journal, June 2016

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journal, July 2015

NaNO2-activated, iron–TEMPO catalyst system for aerobic alcohol oxidation under mild conditions
journal, January 2005

Iron Chloride/4-Acetamido-TEMPO/Sodium Nitrite-Catalyzed Aerobic Oxidation of Primary Alcohols to the Aldehydes
journal, January 2010

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt
journal, April 2011

Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids
journal, June 2016

Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere
journal, February 2016

Iron-Catalyzed Aerobic Oxidation of Alcohols: Lower Cost and Improved Selectivity
journal, March 2019

Metal Nitrate Catalysis for Selective Oxidation of 5-Hydroxymethylfurfural into 2,5-Diformylfuran under Oxygen Atmosphere
journal, April 2019

Tuning the Reactivity of TEMPO by Coordination to a Lewis Acid: Isolation and Reactivity of MCl ₃ (η ¹ -TEMPO) (M = Fe, Al)
journal, November 2012

Oxidation of Alcohols and Activated Alkanes with Lewis Acid-Activated TEMPO
journal, October 2014

Kinetics of Nitroxide Reaction with Iron(II)
journal, September 1999

Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects
journal, November 2015

Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013

Electrochemical studies of acid-promoted disproportionation of nitroxyl radical
journal, May 2003

Equilibrium Acidities of Superacids
journal, January 2011

Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs
journal, November 2017

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character
journal, September 2017

Divergent Reactivity of TEMPO with MBr ₃ (M = B, Al)
journal, April 2013

A kinetics study of the oxidation of iron(II) by nitric acid
journal, May 1980

Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols
journal, October 2011

Efficient Aerobic Oxidation of Secondary Alcohols at Ambient Temperature with an ABNO/NO _x Catalyst System
journal, October 2013

Mechanism of oxidation of primary and secondary alcohols by oxopiperidinium salts
journal, September 1977

Mechanism of the Oxidation of Alcohols by Oxoammonium Cations
journal, June 2007

Multichannel gas-uptake/evolution reactor for monitoring liquid-phase chemical reactions
journal, April 2021

Catalytic Activity Dependency on Catalyst Components in Aerobic Copper-TEMPO Oxidation
journal, September 2009

Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds
journal, February 2014

2-Azaadamantane N -oxyl (AZADO)/Cu Catalysis Enables Chemoselective Aerobic Oxidation of Alcohols Containing Electron-Rich Divalent Sulfur Functionalities
journal, September 2018

Copper catalysis for highly selective aerobic oxidation of alcohols to aldehydes/ketones
journal, January 2019

Iron-Catalysed Selective Aerobic Oxidation of Alcohols to Carbonyl and Carboxylic Compounds
journal, July 2016

Process Development of CuI/ABNO/NMI-Catalyzed Aerobic Alcohol Oxidation
journal, July 2015

Synthesis of HIV-Maturation Inhibitor BMS-955176 from Betulin by an Enabling Oxidation Strategy
journal, April 2017

Development of a Large-Scale Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation for the Synthesis of LSD1 Inhibitor GSK2879552
journal, October 2018