Porous Supramolecular Assemblies for Efficient Suzuki Coupling of Aryl Chlorides

Abstract The development of catalytic systems that can activate aryl chlorides for palladium‐catalyzed cross‐coupling reactions is at the forefront of ongoing efforts to synthesize fine chemicals. In this study, a facile ligand‐template approach is adopted to achieve active‐site encapsulation by forming supramolecular assemblies; this bestowed the pristine inert counterparts with reactivity, which is further increased upon the construction of a porous framework. Experimental results indicated that the isolation of ligands by the surrounding template units is key to the formation of catalytically active monoligated palladium complexes. Additionally, the construction of porous frameworks using the resulting supramolecular assemblies prevented the decomposition of the Pd complexes into nanoparticles, which drastically increased the catalyst lifetime. These findings, along with the simplicity and generality of the synthesis scheme, suggest that the strategy can be leveraged to achieve unique reactivity and potentially enable fine‐chemical synthesis.