[en] A silver-catalyzed cascade conversion of modular alkyne-1,n-diols and carbon dioxide has been developed allowing for the selective formation of keto-functionalized cyclic carbonates. The protocol is characterized by its operational simplicity, excellent scope of carbonate-based heterocycles, and mild reaction conditions. In situ IR studies, control experiments, and detailed computational analysis of these manifolds reveal the intermediacy of an α-alkylidene carbonate that is intercepted by an intramolecular alcohol nucleophile. The synthetic potential of this conceptually attractive CO2 transformation is demonstrated in the preparation of larger ring carbonates and their thermal rearrangement to sterically crowded, five-membered fused carbonate products.
Research center :
Center for Education and Research on Macromolecules (CERM), Belgium Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Belgium
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Li, Xuetong; Barcelona Institute for Science & Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain
Villar-Yanez, Alba; Barcelona Institute for Science & Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain
Ngassam Tounzoua, Charlène ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Benet-Buchholz, Jordi; Barcelona Institute for Science & Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain
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
Bo, Carles; Barcelona Institute for Science & Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain
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
Kleij, Arjan W.; Barcelona Institute for Science & Technology (BIST), Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain > Catalan Institute for Research and Advanced Studies (ICREA), Barcelona, Spain
Language :
English
Title :
Cascade transformation of carbon dioxide and alkyne-1,n-diols into densely substituted cyclic carbonates
Publication date :
15 February 2022
Journal title :
ACS Catalysis
eISSN :
2155-5435
Publisher :
American Chemical Society, Washington DC, United States - Washington
Volume :
12
Issue :
5
Pages :
2854-2860
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
Generalitat de Catalunya [ES] CSC - Chinese Scholarship Council [CN] MINECO - Gobierno de Espana. Ministerio de Economia y Competitividad [ES] F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen [BE] EOS - The Excellence Of Science Program [BE] FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE]
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Further details are provided in CCDC 2088491, 2088492 and 2112335.
In the last two reactions of Table 1, a much lower chemoselectivity towards the keto-carbonate 2a was observed, with various unidentified products in the crude mixture.
The Gaussian 16 program was used with implemented functional and basis set PBE0-D3(BJ)/SDD/def2tzv being chosen (14,18,19) using dispersion correction with Becke-Johnson damping. (20,21) All calculations were carried out at 298 K using an acetonitrile solvent model SMD. Full access to the computational data is provided through: http://dx.doi.org/10.19061/iochem-bd-1-214.
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