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

Abstract

The catalytic hydrogenation of amides is an atom economical method to synthesize amines. Previously, it was serendipitously discovered that the combination of a secondary amide co-catalyst with (iPrPNP)Fe(H)(CO) (iPrPNP = N[CH2CH2(PiPr2)]2-), results in a highly active base metal system for deaminative amide hydrogenation. In this article, we use DFT to develop an improved co-catalyst for amide hydrogenation. Initially, we computationally evaluated the ability of a series of co-catalysts to accelerate the turnover-limiting proton transfer during C–N bond cleavage and poison the (iPrPNP)Fe(H)(CO) catalyst through a side reaction. TBD (triazabicyclodecene) was identified as the leading co-catalyst. It was experimentally confirmed that when TBD is combined with (iPrPNP)Fe(H)(CO) a remarkably active system for amide hydrogenation is generated. TBD also enhances the activity of other catalysts for amide hydrogenation and our results provide guidelines for the rational design of future co-catalysts.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, N-0315 Oslo, Norway
  2. Department of Chemistry, University of Missouri, Columbia, USA
  3. Department of Chemistry, Yale University, New Haven, USA
  4. Department of Electronics, ETSIT, University of Valladolid, 47011 Valladolid, Spain
Publication Date:
Research Org.:
Univ. of Missouri, Columbia, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1595161
Alternate Identifier(s):
OSTI ID: 1594890
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.
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. doi:10.1039/C9SC03812D.
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. doi:10.1039/C9SC03812D.
@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 = {The catalytic hydrogenation of amides is an atom economical method to synthesize amines. Previously, it was serendipitously discovered that the combination of a secondary amide co-catalyst with (iPrPNP)Fe(H)(CO) (iPrPNP = N[CH2CH2(PiPr2)]2-), results in a highly active base metal system for deaminative amide hydrogenation. In this article, we use DFT to develop an improved co-catalyst for amide hydrogenation. Initially, we computationally evaluated the ability of a series of co-catalysts to accelerate the turnover-limiting proton transfer during C–N bond cleavage and poison the (iPrPNP)Fe(H)(CO) catalyst through a side reaction. TBD (triazabicyclodecene) was identified as the leading co-catalyst. It was experimentally confirmed that when TBD is combined with (iPrPNP)Fe(H)(CO) a remarkably active system for amide hydrogenation is generated. TBD also enhances the activity of other catalysts for amide hydrogenation and our results provide guidelines for the rational design of future co-catalysts.},
doi = {10.1039/C9SC03812D},
journal = {Chemical Science},
number = 8,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9SC03812D

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Cited by: 1 work
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Works referenced in this record:

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

  • Artús Suàrez, Lluís; Culakova, Zuzana; Balcells, David
  • ACS Catalysis, Vol. 8, Issue 9
  • DOI: 10.1021/acscatal.8b02184

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

  • Cabrero-Antonino, Jose R.; Alberico, Elisabetta; Drexler, Hans-Joachim
  • ACS Catalysis, Vol. 6, Issue 1
  • DOI: 10.1021/acscatal.5b01955

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


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

  • Magano, Javier; Dunetz, Joshua R.
  • Organic Process Research & Development, Vol. 16, Issue 6
  • DOI: 10.1021/op2003826

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

  • Adam, Rosa; Alberico, Elisabetta; Baumann, Wolfgang
  • Chemistry - A European Journal, Vol. 22, Issue 14
  • DOI: 10.1002/chem.201504709

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


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

  • Smith, Andrew M.; Whyman, Robin
  • Chemical Reviews, Vol. 114, Issue 10
  • DOI: 10.1021/cr400609m

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

  • Garg, Jai Anand; Chakraborty, Subrata; Ben-David, Yehoshoa
  • Chemical Communications, Vol. 52, Issue 30
  • DOI: 10.1039/C6CC01505K

COPASI--a COmplex PAthway SImulator
journal, October 2006


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

  • Zhang, Guoqi; Hanson, Susan K.
  • Chemical Communications, Vol. 49, Issue 86
  • DOI: 10.1039/c3cc45900d

Rethinking the Dehydrogenative Amide Synthesis
journal, September 2017


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

  • John, Jeremy M.; Bergens, Steven H.
  • Angewandte Chemie International Edition, Vol. 50, Issue 44
  • DOI: 10.1002/anie.201103137

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

  • Zhang, Guoqi; Scott, Brian L.; Hanson, Susan K.
  • Angewandte Chemie International Edition, Vol. 51, Issue 48
  • DOI: 10.1002/anie.201206051

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

  • Balaraman, Ekambaram; Gnanaprakasam, Boopathy; Shimon, Linda J. W.
  • Journal of the American Chemical Society, Vol. 132, Issue 47, p. 16756-16758
  • DOI: 10.1021/ja1080019

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


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

  • Rezayee, Nomaan M.; Huff, Chelsea A.; Sanford, Melanie S.
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja511329m

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

  • Bornschein, Christoph; Gustafson, Karl P. J.; Verho, Oscar
  • Chemistry - A European Journal, Vol. 22, Issue 33
  • DOI: 10.1002/chem.201601793

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

  • Zhang, Guoqi; Scott, Brian L.; Hanson, Susan K.
  • Angewandte Chemie, Vol. 124, Issue 48
  • DOI: 10.1002/ange.201206051