[en] The catalyst-free synthesis of urethanes from cyclic iminocarbonates, used as masked isocyanates, and soft nucleophiles (i.e. carboxylic acids and thiols) has been studied. Remarkably, the ring-opening reaction was fully site-selective (i.e. methylene). The disclosed method showed high functional group tolerance towards carboxylic acids bearing alkyl-, alkenyl-, ketone-, pyrone- and hydroxyl groups. This method- ology was further applied for the construction of regioregular functional polyurethanes by step-growth copolymerization of cyclic bisiminocarbonates and dicarboxylic acids or dithiols. Mw up to 34000 g mol−1 was obtained in a fully atom-economical manner using an equimolar amount of both monomers.
Research Center/Unit :
Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
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), Federation of Researcher in Innovative Technologies for CO2 Transformation (FRITCO2T technology platform)
Mampuys, Pieter ; University of Antwerp, Department of Chemistry, Organic Synthesis Division, Belgium
Escudero, Julien; University of Antwerp, Department of Chemistry, Organic Synthesis Division, Belgium
Masullo, Dario; University of Antwerp, Department of Chemistry, Organic Synthesis Division, Belgium
Lemière, Filip; University of Antwerp, Department of Chemistry, Organic Synthesis Division, Belgium
Maes, Bert U. W. ; University of Antwerp, Department of Chemistry, Organic Synthesis Division, 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 :
Functional regioregular (poly)urethanes from soft nucleophiles and cyclic iminocarbonates
Publication date :
08 November 2022
Journal title :
Polymer Chemistry
ISSN :
1759-9954
eISSN :
1759-9962
Publisher :
Royal Society of Chemistry
Volume :
13
Issue :
48
Pages :
6599 - 6605
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique FWO - Flemish Research Foundation EOS - The Excellence Of Science Program
Funding text :
The authors thank the “Fonds National pour la Recherche Scientifique” (F.R.S.-FNRS) and the Fonds Wetenschappelijk Onderzoek – Vlaanderen (FWO) for financial support in the frame of the EOS project no. O019618F (ID EOS: 30902231). B. U. W. M. acknowledges FWO for financial support via research project G0A3517N. C. D. is FNRS Research Director and thanks FNRS for funding. B. U. W. M. acknowledges the Francqui Foundation for an appointment as a Collen-Francqui professor.The authors thank the “Fonds National pour la Recherche Scientifique” (F.R.S.-FNRS) and the Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO) for financial support in the frame of the EOS project no. O019618F (ID EOS: 30902231). B. U. W. M. acknowledges FWO for financial support via research project G0A3517N. C. D. is FNRS Research Director and thanks FNRS for funding. B. U. W. M. acknowledges the Francqui Foundation for an appointment as a Collen-Francqui professor.
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