Functionalized Phosphorus‐Doped Porous Organic Polymers (FPPOPs) ‐Promoted Pd‐Catalyzed Arylation of Hydrosilanes

Abstract The development of novel catalyst systems, especially as highly efficient heterogeneous catalysts for Si−C bond ‐forming arylation reaction of hydrosilanes is highly desirable. Herein, we developed a simple and eco‐friendly methodology for construction of functionalized phosphorus‐doped porous organic polymers (FPPOPs) and its heterogeneous palladium catalyst through anchoring on FPPOPs bearing a phosphine ligand, in which the fabrication of FPPOPs was completed through the vinyl‐substituted triphenylphosphine (ViPPh 3 ) and vinyl‐substituted polyhedral oligomeric silsequioxane (ViPOSS) as well as functional olefins via radical co‐polymerization. All these FPPOPs could act as a phosphine ligand for Pd‐catalyzed arylation of hydrosilanes have been characterized by SEM, FTIR, and X‐RAD. Moreover, the POSS‐based functionalized phosphorus‐doped porous organic polymers (POSS‐PPOPs) proved to be a high efficiency catalyst system for Si−C bond ‐forming arylation of hydrosilanes with aryl iodides and with good yields as well as excellent chemoselectivity with low amount of catalyst under mild conditions. The mechanistic studies supported the effect of functional group on the catalytic activity of Pd/FPPOPs catalyst, which revealed that the weak coordination as well as non‐covalent interaction between porous organic polymers and substrate played important role in the enhancement of chemoselectivity.