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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[CH 2CH 2(P iPr 2)] 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 [5]
  1. Univ. of Oslo (Norway)
  2. Univ. of Missouri, Columbia, MO (United States)
  3. Yale Univ., New Haven, CT (United States)
  4. Univ. of Valladolid (Spain)
  5. Univ. of Oslo (Norway); Arctic Univ. of Norway, Tromsø (Norway)
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; USDOE
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 ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

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 States: 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 States. doi:10.1039/C9SC03812D.
Artús Suàrez, Lluís, Jayarathne, Upul, Balcells, David, Bernskoetter, Wesley H., Hazari, Nilay, Jaraiz, Martín, and Nova, Ainara. Mon . "Rational selection of co-catalysts for the deaminative hydrogenation of amides". United States. 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 = ,
volume = ,
place = {United States},
year = {2020},
month = {1}
}

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

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