[en] The synthesis of dialkyl carbonates, versatile compounds with appli- cations in organic synthesis, pharmaceuticals, and polymers, has at- tracted considerable attention due to their environmentally benign nature. Here, we describe the selective bimolecular nucleophilic substitution (SN2) reaction between primary and secondary alkyl iodides with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-based carbon dioxide-binding organic liquids. We show that TBD is a great candi- date for bulk carbon dioxide and alcohol binding at 100°C. TBD- based carbonate salts are selective for SN2 processes, allowing them to work with highly reactive alkyl iodide while eliminating unwanted base quaternization either in acetonitrile or in bulk at both 21°Cand 65°C. The high reactivity of these TBD-based carbon dioxide-binding organic liquids toward backside SN2 processes at low temperature is explained by the presence of the TBD.H+ guanidinium, revealing a unique metal-free cation-assisted SN2 ion-pair process.
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 :
Delcorps, Juliette; University of Mons [UMons] - Center of Innovation and Research in Materials and Polymers [CIRMAP] - Laboratory of Polymeric and Composite Materials - Belgium
Rawat, Kuber Singh; University of Gent [UGent] - Center for Molecular Modeling - Belgium
Wells, Mathilde; University of Mons [UMons] - Faculty of Medicine and Pharmacy - Laboratory of Pharmaceutical Analysis - Belgium
Ben Ayed, Emna; University of Mons [UMons] - Center of Innovation and Research in Materials and Polymers [CIRMAP] - Laboratory of Polymeric and Composite Materials - 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
Blankert, Bertrand; University of Mons [UMons] - Faculty of Medicine and Pharmacy - Laboratory of Pharmaceutical Analysis - Belgium
Gerbaux, Pascal; University of Mons [UMons] - Organic Synthesis and Mass Spectrometry Laboratory - Belgium
Van Speybroeck, Veronique; University of Gent [UGent] - Center for Molecular Modeling - Belgium
Coulembier, Olivier ; University of Mons [UMons] - Center of Innovation and Research in Materials and Polymers [CIRMAP] - Laboratory of Polymeric and Composite Materials - Belgium
Language :
English
Title :
Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 ion-pair process
Publication date :
June 2024
Journal title :
Cell Reports. Physical Science
eISSN :
2666-3864
Publisher :
Elsevier BV
Pages :
102057
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique
Funding text :
J.D. and E.B.A. acknowledge the support of the AXA Research Fund for the funding of this project. O.C. acknowledges support for his position as a senior research asso- ciate for the F.R.S.-FNRS of Belgium and AXA Professor in Chemistry. K.S.R. and V.V.S. acknowledge the research board of UGent (Bijzonder Onderzoeksfonds) through a Concerted Research Action (GOA010-17). The computational resources and services (Stevin Supercomputer Infrastructure) were provided by the VSC (Flem- ish Supercomputer Center), funded by UGent, Research Foundation Flanders, and the Flemish Government-department EWI. C.D. is the FNRS Research Director and thanks FNRS for financial support.
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