Organic porous heterogeneous composite with antagonistic catalytic sites as a cascade catalyst for continuous flow reaction.

One-pot cascade catalytic reactions easily allow the circumvention of pitfalls of traditional catalytic reactions, such as multi-step syntheses, longer duration, waste generation, and high operational cost. Despite advances in this area, the facile assimilation of chemically antagonistic bifunctional sites in close proximity inside a well-defined scaffold a process of rational structural design still remains a challenge. Herein, we report the successful fusion of incompatible acid-base active sites in an ionic porous organic polymer (iPOP), 120-MI@OH, a simple ion-exchange strategy. The fabricated polymer catalyst, 120-MI@OH, performed exceedingly well as a cascade acid-base catalyst in a deacetylation-Knoevenagel condensation reaction under mild and eco-friendly continuous flow conditions. In addition, the abundance of spatially isolated distinct acidic (imidazolium cations) and basic (hydroxide anions) catalytic sites give 120-MI@OH its excellent solid acid and base catalytic properties. To demonstrate the practical relevance of 120-MI@OH, stable millimeter-sized spherical composite polymer bead microstructures were synthesized and utilized in one-pot cascade catalysis under continuous flow, thus illustrating promising catalytic activity. Additionally, the heterogeneous polymer catalyst displayed good recyclability, scalability, as well as ease of fabrication. The superior catalytic activity of 120-MI@OH can be rationalized by its unique structure that reconciles close proximity of antagonistic catalytic sites that are sufficiently isolated in space.