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Imidazolium‐Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer‐Supported N ‐Heterocyclic Carbenes for Organocatalysis
Author(s) -
Lambert Romain,
Coupillaud Paul,
Wirotius AnneLaure,
Vignolle Joan,
Taton Daniel
Publication year - 2016
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201600019
Subject(s) - chemistry , deprotonation , polymer chemistry , ionic liquid , electrophile , methyl methacrylate , catalysis , organic chemistry , methyl acrylate , organocatalysis , vinyl acetate , transesterification , polymer , copolymer , ion , enantioselective synthesis
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‐CS 2 units by chemical postmodification of acetate‐containing coPILs, in the presence of CS 2 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.