title: Imidazolium-Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer-Supported N-Heterocyclic Carbenes for Organocatalysis.
abstract: Statistical copoly(ionic liquid)s (coPILs), namely, poly(styrene)-co-poly(4-vinylbenzylethylimidazolium acetate) are synthesized by free-radical copolymerization in methanolic solution. These coPILs serve to in situ generate polymer-supported N-heterocyclic carbenes (NHCs), referred to as polyNHCs, due to the noninnocent role of the weakly basic acetate counter-anion interacting with the proton in C2-position of pendant imidazolium rings. Formation of polyNHCs is first evidenced through the quantitative formation of NHC-CS2 units by chemical postmodification of acetate-containing coPILs, in the presence of CS2 as electrophilic reagent (= stoichiometric functionalization of polyNHCs). The same coPILs are also employed as masked precursors of polyNHCs in organocatalyzed reactions, including a one-pot two-step sequential reaction involving benzoin condensation followed by addition of methyl acrylate, cyanosilylation, and transesterification reactions. The catalytic activity can be switched on and off successively upon thermal activation, thanks to the deprotonation/reprotonation equilibrium in C2-position. NHC species are thus in situ released upon heating at 80 °C (deprotonation), while regeneration of the coPIL precursor occurs at room temperature (reprotonation), triggering its precipitation in tetrahydrofuran. This also allows recycling the coPIL precatalyst by simple filtration, and reusing it for further catalytic cycles. The different organocatalyzed reactions tested can thus be performed with excellent yields after several cycles.
authors.affiliation: Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, IPB-ENSCBP, F-33607, Pessac Cedex, France.|Laboratoire de Chimie des Polymères Organiques, Centre National de la Recherche Scientifique, 16 Avenue Pey-Berland, F-33607, Pessac Cedex, France.
authors.forename: Romain
authors.initials: R
authors.lastname: Lambert
authors.affiliation: Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, IPB-ENSCBP, F-33607, Pessac Cedex, France.|Laboratoire de Chimie des Polymères Organiques, Centre National de la Recherche Scientifique, 16 Avenue Pey-Berland, F-33607, Pessac Cedex, France.
authors.forename: Paul
authors.initials: P
authors.lastname: Coupillaud
authors.affiliation: Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, IPB-ENSCBP, F-33607, Pessac Cedex, France.|Laboratoire de Chimie des Polymères Organiques, Centre National de la Recherche Scientifique, 16 Avenue Pey-Berland, F-33607, Pessac Cedex, France.
authors.forename: Anne-Laure
authors.initials: AL
authors.lastname: Wirotius
authors.affiliation: Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, IPB-ENSCBP, F-33607, Pessac Cedex, France.|Laboratoire de Chimie des Polymères Organiques, Centre National de la Recherche Scientifique, 16 Avenue Pey-Berland, F-33607, Pessac Cedex, France.
authors.forename: Joan
authors.initials: J
authors.lastname: Vignolle
authors.affiliation: Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, IPB-ENSCBP, F-33607, Pessac Cedex, France.|Laboratoire de Chimie des Polymères Organiques, Centre National de la Recherche Scientifique, 16 Avenue Pey-Berland, F-33607, Pessac Cedex, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Taton
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D002384:Catalysis; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
chemical_list: D000085:Acetates; D000838:Anions; D006571:Heterocyclic Compounds; D007093:Imidazoles; D052578:Ionic Liquids; D011108:Polymers; C030011:carbene; D008697:Methane
keywords: N-heterocyclic carbenes; imidazolium; organocatalysis; poly(ionic liquid)s