# Advances in Organic and Organic-Inorganic Hybrid Polymeric Supports for Catalytic Applications
## 4 Metal-Catalysed Non-Asymmetric Reactions
### Miscellaneous Examples
The effect of these different supports on the mean reaction rate was studied by a Design of Experiments (DoE) based on the Taguchi methods [102], carrying out the 1-phenylethanol oxidation reaction at two different temperatures (100 and 150 \({}^{\circ}\)C) and several reaction times (15, 30, 60 and 120 min). The DoE analysis suggested that the increase of the chain length on the imidazolium, following the order -Me, -But and -Dec, led to an enhancement of the reaction rate. This trend also matched the one observed for AuNPs size distribution. Increasing the length of alkyl chain, a bigger AuNPs size distribution was observed. The larger reaction rates were found for AuNPs-SILLPs based on macroporous resins. The effect of the ionic liquid loading was the least pronounced. The DoE analysis also indicated that in many cases there was an enhancement of the catalytic efficiency with the increase of AuNPs sizes. Finally the reusability of the AuNPs-SILLPs was evaluated by testing AuNPs-SILLP **160b**. The catalytic activity decreased for consecutive uses from 67% to 39%, 37% and 35% for the 2 nd-4 th cycles, because of the lixiviation of the active metal species from the stabilized NPs. In order to improve the applicability of these catalytic systems, a polymer cocktail containing the initial catalytic composite AuNPs-SILLPs **160b** along with the corresponding basic SILPs (R = Dec. X = OH-, macro, 3.45 mmol OH-/g), which acted simultaneously as a scavenger for the lixiviated species and as a base to modify the catalytic process, was evaluated. A positive effect was observed. The yield in the first cycle increased in comparison with the reaction performed in the absence of the basic SILLP (82% vs. 67%) and the catalytic activity decreased at a lower extent (73% for the 2 nd, 58% for the 3 rd and 45% for the 4 th use). Finally, synthesis of some PdNPs-SILLPs was also performed. Under similar conditions, catalytic activity of AuNPs-SILLPs was proved to be better than that of PdNPs-SILLPs. Recently, the polystyrene-linked tris(triazolyl)methanecopper (I) cationic catalyst **162** was reported for the general carbene transfer reaction in batch and flow reactions [103]. It was prepared by reaction between the polystyrene-supported tris(triazolyl) methyl complex **161** and [Cu(MeCN)4][PF6] in dichloromethane at room temperature (Scheme 62). It was applied, in 5.2 mol % loading, in the reaction of ethyl diazoacetate (EDA) with six substrates under batch conditions, obtaining high yields. The recyclability is evaluated in each reaction. The catalyst was separated by filtration and reused for five consecutive reaction cycles, keeping the reaction time constant. Essentially constant yields were observed; a slight decrease was noticed only with less reactive cyclohexane in the C-H bond insertion reaction. Furthermore, these six reactions were also carried out with a single catalyst sample in a sequential manner. Each reaction was repeated two times, and no decrease in activity was detected in twelve consecutive experiments. Then, the catalytic system was also investigated in continuous flow. Under optimized reaction conditions involving a flow rate as high as 500 \(\mu\)L min-1 (equivalent to 1 min residence time), the preparation of small libraries of compounds was carried out by reaction of five different substrates with EDA. Four different types of carbene transfer (O-H insertion, N-H insertion, C-H insertion and cyclopropenation) in a sequential manner were carried out. Except for the cyclopropenation case, productivities in flow were significantly higher (up to four times) than those recorded for the same reactions in batch.