# Advances in Organic and Organic-Inorganic Hybrid Polymeric Supports for Catalytic Applications
## 4 Metal-Catalysed Non-Asymmetric Reactions  
### Epoxidation of Alkenes  
In 2014, [PERSON] et al. reported the first amphiphilic polyoxometalate(POM)-paired ionic polymer-based heterogeneous epoxidation system [61]. The new amphiphilic POM-paired ionic copolymer **102** was prepared by anion-exchange of functionalized-ionic liquid copolymer **101** with the [PO\({}_{4}\)(WO\({}_{3}\))\({}_{4}\)]\({}^{3-}\) species (Scheme 35). Copolymer **101** was synthesized by the free radical copolymerization of 3-dodecyl-1-vinylimidazolium bromide and 3-propionic acid-1-vinyl-imidazolium bromide using AIBN as initiator. The catalytic performance of catalyst **102** was evaluated in the epoxidation of various alkenes with H\({}_{2}\)O\({}_{2}\) as oxidant and ethyl acetate as solvent. Liquid-liquid-solid three-phase reaction systems were observed and good to excellent conversions (48%-100%) were obtained. The reusability of catalyst **102** was studied in epoxidation of cyclooctene and 1-octene. The catalyst was recovered by filtration and reused for five cycles. A slight gradual loss of activity was observed, while the selectivity was preserved. The results of ICP-AES elemental analysis for the reacted filtrate showed that less than 1.6 wt % of the total W in the catalyst leached into the reaction media. This could have led to the gradual decrease in activity observed in the recycling tests. In the same year, epoxidation of olefins with H\({}_{2}\)O\({}_{2}\) was also carried out in presence of the amphiphilic composite **106**, constituted by a magnetic Fe\({}_{3}\)O\({}_{4}\) core and a dodecylamine-modified  
Figure 34: Synthesis of PS-squaramide **100** and its application in the enantioselective flow synthesis of pyranonaphthoquinones. polyoxometalate-paired poly-(ionic liquid) shell [62]. The material **106** was prepared in the following way (Scheme 36). First, the 3-propionic acid-1-vinylimidazolium chloride was adsorbed on Fe\({}_{3}\)O\({}_{4}\) surface via chemisorption interaction between the functional group -COOH and iron ion (see material **103**). Next, the polymerization of the vinyl imidazole ionic liquid in presence of potassium peroxolsulfate (KPS) led to poly-(ionic liquid) coating on Fe\({}_{3}\)O\({}_{4}\) core **104**. **Scheme 35. Preparation of POM-paired ionic polymer **102** and its use in the epoxidation of alkenes. **Scheme 36. Preparation of catalyst **106** and its application in the epoxidation of alkenes. Afterward, the anion-exchange of poly-(ionic liquid) network with H\({}_{3}\)PW\({}_{12}\)O\({}_{40}\), followed by treatment with dodecylamine, provided the material **106**. In presence of **106** as catalyst and acetonitrile as solvent, high conversion values (77%-100%) and selectivities (95%-100%) were obtained. The catalytic reusability was studied in epoxidation of D,L-limonene. After the reaction, the catalyst was easily separated by an external magnet. The recovered catalyst showed a slow decrease in activity (89% conversion) in the third run but the initial catalytic activity (95% conversion) was restored after treatment with dodecylamine. The result of ICP-AES analysis showed that less than 0.9 wt % of W has been leached into the reaction media. Recent studies have shown that the incorporation of POSS into organic or inorganic polymer could create a micro/mesoporous matrix without using a template [63; 64]. In light of this and taking into account that porous framework structure of the solid catalysts would favour the increase of their catalytic performances, [PERSON] et al. reported the synthesis of POSS-derived mesoporous poly(ionic liquids) **109a-e** in order to obtain the amphiphilic mesostructured polyoxometalate-based ionic hybrids **110a-e** (Scheme 37) [65]. The introduction of the POSS unit could permit to control the pore structure and wettability of material.