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  4. Pivotal Role of the Basic Character of Organic and Salt Catalysts in C-N Bond Forming Reactions of Amines with CO2
 
review article

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C-N Bond Forming Reactions of Amines with CO2

Hulla, Martin  
•
Dyson, Paul J.  
2020
Angewandte Chemie International Edition

Organocatalysts promote a range of C-N bond forming reactions of amines with CO2. Herein, we review these reactions and attempt to identify the unifying features of the catalysts that allows them to promote a multitude of seemingly unrelated reactions. Analysis of the literature shows that these reactions predominantly proceed by carbamate salt formation in the form [BaseH][RR ' NCOO]. The anion of the carbamate salt acts as a nucleophile in hydrosilane reductions of CO2, internal cyclization reactions or after dehydration as an electrophile in the synthesis of urea derivatives. The reactions are enhanced by polar aprotic solvents and can be either promoted or hindered by H-bonding interactions. The predominant role of all types of organic and salt catalysts (including ionic liquids, ILs) is the stabilization of the carbamate salt, mostly by acting as a base. Catalytic enhancement depends on the combination of the amine, the base strength, the solvent, steric factors, ion pairing and H-bonding. A linear relationship between the base strength and the reaction yield has been demonstrated with IL catalysts in the synthesis of formamides and quinazoline-2,4-diones. The role of organocatalysts in the reactions indicates that all bases of sufficient strength should be able to catalyze the reactions. However, a physical limit to the extent of a purely base catalyzed reaction mechanism should exist, which needs to be identified, understood and overcome by synergistic or alternative methods.

  • Details
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Type
review article
DOI
10.1002/anie.201906942
Web of Science ID

WOS:000486411000001

Author(s)
Hulla, Martin  
Dyson, Paul J.  
Date Issued

2020

Publisher

Wiley-VCH Verlag GmbH

Published in
Angewandte Chemie International Edition
Volume

59

Issue

3

Start page

1002

End page

1017

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

c1 synthon

•

carbon dioxide

•

organic synthesis

•

organocatalysis

•

sustainable chemistry

•

solvent-free synthesis

•

environmentally benign access

•

carbon-dioxide

•

efficient synthesis

•

chemical fixation

•

ionic liquids

•

reductive functionalization

•

heterocyclic carbene

•

carboxylative cyclization

•

straightforward route

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCOM  
Available on Infoscience
September 29, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/161660
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