TEMPO was immobilized on continuous-flow-optimized mesoporous silica particles and a TEMPO/DAIB mediated oxidation followed by Knoevenagel condensation was investigated.

We report the immobilization of 4-dimethylaminopyridine (DMAP), a versatile organocatalyst for sterically demanding esterifications, on mesoporous silica particles and macromesoporous silica monoliths, both possessing optimized properties for continuous flow synthesis. An alkyne-functionalized DMAP derivative was immobilized via click chemistry; the materials were characterized by physisorption analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and elemental analysis. While silica particles were functionalized in batch and packed into a packed-bed reactor, monoliths were cladded with a polyether ether ketone (PEEK) tube after sol-gel synthesis and functionalized in a circulating flow process. Samples with three different catalyst loadings were prepared, in order to study the impact of the catalyst amount on the mesopore space as well as the catalytic performance. In continuous flow experiments, complete conversion of 1-phenylethanol to phenylethylacetate was achieved with both materials and short contact times. Monoliths exhibited far lower pressures than packed bed reactors (7 bar at a flow rate of 1 mL min À 1 ) and reached turnover rates up to 9.3x10 À 2 s À 1 , which is almost twice as high as a comparable batch experiment. The absence of diffusion limitations in monoliths made investigations on reaction kinetics with microkinetics-dominated experiments possible. This study demonstrates that all properties needed for a successful transfer of immobilized organocatalysts to sophisticated flow syntheses with complex organocatalysts can be met with functionalized meso-macroporous monoliths.