Synthesis of Polyfluorinated Biaryls via Palladium-Catalyzed Decarboxylative Cross-Coupling of Zinc Polyfluorobenzoates with Aryl Fluorosulfates

A palladium-catalyzed decarboxylative cross-coupling of zinc polyfluorobenzoates with aryl fluorosulfates, which proceeded efficiently via C-O bond cleavage to afford the corresponding polyfluorinated biaryls in moderate-to-good yields, was developed. The reactions exhibited both good substrate scope and broad functional group compatibility, and it could be scaled-up easily. The synthetic simplicity and practicability of the reaction was further demonstrated by one-pot manipulation by directly mixing polyfluorobenzoic acid and Zn(OH)₂ in the coexistence of aryl fluorosulfate and a palladium catalyst in one flask. Further studies showed that aryl fluorosulfate is more robust than other aryl halides and pseudohalides as a arylating reagent, and zinc polyfluorobenzoate is a more effective decarboxylative polyfluoroarylating agent than their magnesium and potassium counterparts.