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:
-
[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:
- 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}
}
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DOI: 10.1039/C9SC03812D
DOI: 10.1039/C9SC03812D
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