Nickel-Catalyzed Decarbonylative Cou­pling of Aryl Esters and Arylboronic Acids

A variety of functionalized biaryls can be accessed by coupling aryl and heteroaryl esters with boronic acids in Suzuki–Miyaura‐type decarbonylative cross‐coupling catalyzed by an affordable catalyst system composed of Ni(cod)2 and PCy3. The methodology is tolerant of a variety of functional groups and presents an attractive alternative to the use of palladium catalysis currently used in industry to acquire such bis(hetero)aryls, but also reveals challenges associated with nickel catalysis of esters in cross‐coupling chemistry. Functionalized bis(hetero)aryl motifs are easily accessed from heteroaryl esters and boronic acids by using decarbonylative coupling. The Suzuki–Miyaura‐type cross‐coupling is catalyzed by an affordable low‐toxic catalyst system composed of Ni(cod)2 and PCy3. This methodology presents an attractive alternative to the use of palladium catalysts currently used in industry to acquire bis(hetero)aryls.