Catalyst‐Free Thia‐Michael Addition to alpha‐Trifluoromethylacrylates for 3D Network Synthesis
Résumé
Thia-Michael additions (1,4-additions of a thiol to a Michael acceptor) are generally catalyzed by an external Brønsted or Lewis base. A spontaneous (uncatalyzed) Michael addition of thiols to a-trifluoromethyl acrylates is described in this article, as well as its application to the very efficient preparation of a thermoset. A thorough mechanistic investigation, based on an experimental kinetic study and on DFT calculations, is presented for the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents, unveiling a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF3 group.
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Berne, Catalyst-Free Thia-Michael Addition , 2023.pdf (1.55 Mo)
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