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Updated: Aug 14, 2025

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction
Published on: January 19, 2016
Catalyst-Free Thia-Michael Addition to α-Trifluoromethylacrylates for 3D Network Synthesis
Dimitri Berne1, Sébastien Lemouzy1, Pascale Guiffrey1
1ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France.
Abstract:
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 α-trifluoromethyl acrylates is described, 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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