Abstract :
[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.
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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