Rational selection of co-catalysts for the deaminative hydrogenation of amides

Artús Suàrez, Lluís; Jayarathne, Upul; Balcells, David; Bernskoetter, Wesley H.; Hazari, Nilay; Jaraiz, Martín; Nova, Ainara

doi:10.1039/C9SC03812D

Title: Rational selection of co-catalysts for the deaminative hydrogenation of amides

Abstract

Theory and experiments were used to rationally design co-catalysts for the deaminative hydrogenation of amides. TBD was found to be the optimal catalyst, assisting the C–N bond cleavage while preventing the formation of adducts with the catalyst.

Authors:

^[1]; Jayarathne, Upul ^[2]; Balcells, David ^[1];

^[2];

^[3];

^[4];

^[1]

Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, N-0315 Oslo, Norway
Department of Chemistry, University of Missouri, Columbia, USA
Department of Chemistry, Yale University, New Haven, USA
Department of Electronics, ETSIT, University of Valladolid, 47011 Valladolid, Spain

Publication Date:: 2020-02-26

Research Org.:: Univ. of Missouri, Columbia, MO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1595161

Alternate Identifier(s):: OSTI ID: 1594890; OSTI ID: 1777141

Grant/Contract Number:: SC0018222; 250044; 262695; nn4654k; 85378

Resource Type:: Published Article

Journal Name:: Chemical Science

Additional Journal Information:: Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 8; Journal ID: ISSN 2041-6520

Publisher:: Royal Society of Chemistry

Country of Publication:: United Kingdom

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Artús Suàrez, Lluís, Jayarathne, Upul, Balcells, David, Bernskoetter, Wesley H., Hazari, Nilay, Jaraiz, Martín, and Nova, Ainara. Rational selection of co-catalysts for the deaminative hydrogenation of amides.  United Kingdom: N. p., 2020. 
Web.  doi:10.1039/C9SC03812D.

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                    Artús Suàrez, Lluís, Jayarathne, Upul, Balcells, David, Bernskoetter, Wesley H., Hazari, Nilay, Jaraiz, Martín, & Nova, Ainara. Rational selection of co-catalysts for the deaminative hydrogenation of amides.  United Kingdom.  https://doi.org/10.1039/C9SC03812D

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                    Artús Suàrez, Lluís, Jayarathne, Upul, Balcells, David, Bernskoetter, Wesley H., Hazari, Nilay, Jaraiz, Martín, and Nova, Ainara. Wed .  
"Rational selection of co-catalysts for the deaminative hydrogenation of amides".  United Kingdom.  https://doi.org/10.1039/C9SC03812D.

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@article{osti_1595161,

  title        = {Rational selection of co-catalysts for the deaminative hydrogenation of amides},

  author       = {Artús Suàrez, Lluís and Jayarathne, Upul and Balcells, David and Bernskoetter, Wesley H. and Hazari, Nilay and Jaraiz, Martín and Nova, Ainara},

  abstractNote = {Theory and experiments were used to rationally design co-catalysts for the deaminative hydrogenation of amides. TBD was found to be the optimal catalyst, assisting the C–N bond cleavage while preventing the formation of adducts with the catalyst.},

  doi          = {10.1039/C9SC03812D},

  journal      = {Chemical Science},

  number       = 8,

  volume       = 11,

  place        = {United Kingdom},

  year         = {2020},

  month        = {2}

}

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Title: Rational selection of co-catalysts for the deaminative hydrogenation of amides

Abstract

Citation Formats

The Key Role of the Hemiaminal Intermediate in the Iron-Catalyzed Deaminative Hydrogenation of Amides journal, August 2018

Selective Iron-Catalyzed Deaminative Hydrogenation of Amides journal, January 2017

Efficient Base-Free Hydrogenation of Amides to Alcohols and Amines Catalyzed by Well-Defined Pincer Imidazolyl–Ruthenium Complexes journal, November 2015

Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol journal, January 2018

Large-Scale Carbonyl Reductions in the Pharmaceutical Industry journal, April 2012

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions journal, February 2016

Manganese-Catalyzed Sequential Hydrogenation of CO 2 to Methanol via Formamide journal, August 2017

The role of the metal-bound N–H functionality in Noyori-type molecular catalysts journal, November 2018

Organic superbase-induced chemiluminescent decomposition of a hydroxyaryl-substituted dioxetane: Unique effect of a bifunctional guanidine base on the chemiluminescence profile of a bicyclic dioxetane bearing a 4-(benzoxazol-2-yl)-3,5-dihydroxyphenyl moiety journal, March 2018

Review of Methods for the Catalytic Hydrogenation of Carboxamides journal, February 2014

Unprecedented iron-catalyzed selective hydrogenation of activated amides to amines and alcohols journal, January 2016

COPASI--a COmplex PAthway SImulator journal, October 2006

Cobalt-catalyzed transfer hydrogenation of CO and CN bonds journal, January 2013

Rethinking the Dehydrogenative Amide Synthesis journal, September 2017

A Highly Active Catalyst for the Hydrogenation of Amides to Alcohols and Amines journal, August 2011

Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of CC, CO, and CN Bonds journal, October 2012

Direct Hydrogenation of Amides to Alcohols and Amines under Mild Conditions journal, December 2010

First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands journal, October 2018

Theoretical Investigation on Mechanism of the PPh 3 -Catalyzed Isomerization of Allenic Sulfones to 2-Arylsulfonyl 1,3-Dienes: Effects of Additive as the Proton-Shuttle journal, July 2016

Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO 2 to Methanol journal, January 2015

Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols journal, July 2016

A Highly Active Catalyst for the Hydrogenation of Amides to Alcohols and Amines journal, August 2011

Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of CC, CO, and CN Bonds journal, October 2012

The Key Role of the Hemiaminal Intermediate in the Iron-Catalyzed Deaminative Hydrogenation of Amides
journal, August 2018

Selective Iron-Catalyzed Deaminative Hydrogenation of Amides
journal, January 2017

Efficient Base-Free Hydrogenation of Amides to Alcohols and Amines Catalyzed by Well-Defined Pincer Imidazolyl–Ruthenium Complexes
journal, November 2015

Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol
journal, January 2018

Large-Scale Carbonyl Reductions in the Pharmaceutical Industry
journal, April 2012

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
journal, February 2016

Manganese-Catalyzed Sequential Hydrogenation of CO ₂ to Methanol via Formamide
journal, August 2017

The role of the metal-bound N–H functionality in Noyori-type molecular catalysts
journal, November 2018

Organic superbase-induced chemiluminescent decomposition of a hydroxyaryl-substituted dioxetane: Unique effect of a bifunctional guanidine base on the chemiluminescence profile of a bicyclic dioxetane bearing a 4-(benzoxazol-2-yl)-3,5-dihydroxyphenyl moiety
journal, March 2018

Review of Methods for the Catalytic Hydrogenation of Carboxamides
journal, February 2014

Unprecedented iron-catalyzed selective hydrogenation of activated amides to amines and alcohols
journal, January 2016

COPASI--a COmplex PAthway SImulator
journal, October 2006

Cobalt-catalyzed transfer hydrogenation of CO and CN bonds
journal, January 2013

Rethinking the Dehydrogenative Amide Synthesis
journal, September 2017

A Highly Active Catalyst for the Hydrogenation of Amides to Alcohols and Amines
journal, August 2011

Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of CC, CO, and CN Bonds
journal, October 2012

Direct Hydrogenation of Amides to Alcohols and Amines under Mild Conditions
journal, December 2010

First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands
journal, October 2018

Theoretical Investigation on Mechanism of the PPh 3 -Catalyzed Isomerization of Allenic Sulfones to 2-Arylsulfonyl 1,3-Dienes: Effects of Additive as the Proton-Shuttle
journal, July 2016

Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO ₂ to Methanol
journal, January 2015

Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols
journal, July 2016

A Highly Active Catalyst for the Hydrogenation of Amides to Alcohols and Amines
journal, August 2011

Mild and Homogeneous Cobalt-Catalyzed Hydrogenation of CC, CO, and CN Bonds
journal, October 2012