[en] Herein, the long-standing challenge of the ring-opening aminolysis of CO2-derived tetrasubstituted cyclic carbonates at room temperature (r.T) is overcome under catalyst-free conditions. Molecular design of the cyclic carbonate by substitution of an alkyl group by a thioether unlocks quantitative conversion at r.T and ensures total regioselectivity toward highly substituted oxazolidone scaffolds. An in-depth rationalization of the high reactivity of these cyclic carbonate structures and of the aminolysis reaction mechanism is provided by a computational study supporting experimental observations. The high efficiency of the reaction is then translated to the deconstruction of high-performance thermoplastics containing tetrasubstituted cyclic carbonate linkages to deliver building blocks that are reused for designing recyclable thermosets bearing dynamic N,S-acetal linkages.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège CERM - Center for Education and Research on Macromolecules - ULiège
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Habets, Thomas ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Méreau, Raphaël ; University of Bordeaux - Institut des Sciences Moléculaires [ISM] - Bordeaux INP - France
Siragusa, Fabiana ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Grignard, Bruno ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; University of Liège [ULiège] - FRITCO2T Platform - Belgium
Detrembleur, Christophe ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Language :
English
Title :
Fast, Regioselective Aminolysis of Tetrasubstituted Cyclic Carbonates and Application to Recyclable Thermoplastics and Thermosets
Publication date :
19 November 2024
Journal title :
ACS Macro Letters
eISSN :
2161-1653
Publisher :
American Chemical Society (ACS)
Volume :
13
Pages :
1425-1432
Peer reviewed :
Peer Reviewed verified by ORBi
Tags :
CÉCI : Consortium des Équipements de Calcul Intensif
Région Nouvelle-Aquitaine F.R.S.-FNRS - Fonds de la Recherche Scientifique Région wallonne
Funding text :
The authors of Liege thank FNRS for the financial support in the frame of the CO2Switch project under grant T.0075.20. C.D. is a F.R.S.-FNRS Research Director and J.M.R is a F.R.S.-FNRS Senior Research Associate. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 and by the Walloon Region. Computer time was provided by the Pôle Modélisation HPC facilities of the Institut des Sciences Moléculaires UMR 5255 CNRS – Université de Bordeaux, cofunded by the Nouvelle Aquitaine region.
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