Catalysis of Synergistic Reactions by Host–Guest Assemblies: Reductive Carbonylation of Nitrobenzenes

[Image: see text] Numerous chemical transformations require two or more catalytically active sites that act in a concerted manner; nevertheless, designing heterogeneous catalysts with such multiple functionalities remains an overwhelming challenge. Herein, it is shown that by the integration of acidic flexible polymers and Pd-metallated covalent organic framework (COF) hosts, the merits of both catalytically active sites can be utilized to realize heterogeneous synergistic catalysis that are active in the conversion of nitrobenzenes to carbamates via reductive carbonylation. The concentrated catalytically active species in the nanospace force two catalytic components into proximity, thereby enhancing the cooperativity between the acidic species and Pd species to facilitate synergistic catalysis. The resulting host–guest assemblies constitute more efficient systems than the corresponding physical mixtures and the homogeneous counterparts. Furthermore, this system enables easy access to a family of important derivatives such as herbicides and polyurethane monomers and can be integrated with other COFs, showing promising results. This study utilizes host–guest assembly as a versatile tool for the fabrication of multifunctional catalysts with enhanced cooperativity between different catalytic species.