Integrating an Organocatalyst into a Polymeric Gel Framework for the Continuous Microflow Baylis-Hillman Reaction

Continuous flow catalysis utilizing gel-bound organocatalysts within a microfluidic reactor represents a compelling strategy in the realm of organic synthesis. In this study, a quinuclidine-based catalytic monomer (QMA) was synthesized to create polymer gel dots through the process of photopolymerization that serve as a support for the catalyst. The resulting gel-bound organocatalysts were assembled within a continuous microfluidic reactor to facilitate the Baylis-Hillman reaction between various aldehydes and acrylonitrile at a temperature of 50 °C. The conversion of the product was assessed using ¹H NMR spectroscopy as an offline analytical method over a duration of 8 h. The findings indicated that highly reactive aldehydes achieved conversion rates exceeding 90%, in contrast to their less reactive counterparts. Furthermore, these results were juxtaposed with previously published data derived from alternative synthetic methodologies, revealing that the continuous microfluidic reactions employing integrated organocatalysts within polymer networks exhibited significantly higher conversions with reduced reaction times (8 h) at the same temperature (50 °C). Additionally, the influence of different geometries (round, triangular, and square) of the gel dots on catalytic activity was investigated, with round and square gel dots demonstrating slightly superior performance compared with triangular gel dots, attributed to their increased surface area. Moreover, an extended reaction period of 6 days was conducted using 4-bromobenzaldehyde and acrylonitrile, resulting in a conversion rate exceeding 70%, which remained stable for 5 days before experiencing a slight decline due to product accumulation on the gel dots.