Organocatalysis in polysiloxane gels: a magnetic-stir-bar encapsulated catalyst system prepared by thiol–ene photo-click immobilization

Abstract

This manuscript presents a facile thiol–ene photo-click chemistry method to prepare magnetic stir bar-encapsulated polysiloxane-based organocatalyst gels under benign conditions, and develops a Stir Bar-Encapsulated Catalysis (SBEC) technique. Through thiol–ene addition chemistry, we graft olefin-terminated organocatalysts (i.e. MacMillan catalyst, proline catalyst, and N-heterocyclic carbene catalyst) onto poly[3-mercaptopropylmethylsiloxane], which is further photo-crosslinked to coat the embedded magnetic stir bar. The prepared magnetic stir bar-encapsulated polysiloxane-based organocatalyst gels can be put into reaction flasks to perform stirring and catalysis functions at the same time. The most important benefit of SBEC technique is to infinitely simplify the catalyst/product separation procedure by using a simple stir-bar-retriever, even without any precipitation/filtration steps. The catalytic performances of three different organocatalyst gels applied in asymmetric Diels–Alder reaction, asymmetric aldol reaction and benzoin condensation reaction respectively are also examined herein.