Continuous‐Flow Suzuki‐Miyaura Coupling in Water and Organic Solvents Promoted by Blends of Stabilized Convoluted Polymeric Palladium Catalysts and Polymeric Auxiliary Materials

Abstract

Given that heterogeneous palladium‐catalyzed C−C bond formation reactions under continuous‐flow conditions are well suited for the efficient and safe production of pharmaceuticals and functional materials, the development of active and durable catalysts for this purpose is a matter of high practical significance. Here, a previously established molecular convolution methodology was used to synthesize catalysts for Suzuki‐Miyaura coupling under flow conditions by blending convoluted polymeric palladium catalysts (prepared from copolymers of 4‐vinylpyridine and 4‐tert‐butylstyrene) and crosslinked polymeric auxiliary materials (prepared from copolymers of divinylbenzene and 4‐tert‐butylstyrene). The optimal catalyst exhibited high performance and durability and allowed numerous biaryl products such as liquid‐crystalline materials, organic electroluminescent materials, and pharmaceuticals to be continuously synthesized with turnover frequencies of up to 238 h−1. In a demonstration of practical utility, the developed catalytic system was used for the continuous synthesis of two pharmaceuticals (felbinac and fenbufen) in water as the sole solvent.