Nickelâ Catalyzed Crossâ Coupling of (Hetero)aryl Chlorides with Aryllithium Compounds

Abstract

The nickel pincer complexes [Ni(Cl){N(2â R2PC6H4)(2â ²â Me2NC6H4)}] (R=Ph, 1â a; R=iPr, 1â b; R=Cy, 1â c) were demonstrated to catalyze crossâ coupling of aryl or heteroaryl chlorides with aryllithium compounds under mild reaction conditions. The catalytic activity of 1â a was highest and resulted in biaryl products in 23â 96â % yields. A series of aryl chlorides including deactivated ones, such as 1â chloroâ 4â methoxybenzene, 4â chloroâ N,Nâ dimethylaniline, and 1â chloroâ 4â methylbenzene, and heteroaryl chlorides, including 2â and 3â chloropyridine, 2â chloroâ 4â methylquinoline, 2â chlorothiophene, 2â chlorobenzofuran, 2â chlorobenzo[d]oxazole, and 2â chlorobenzo[d]thiazole, were used in this coupling reaction.Nick and pin: The crossâ coupling of aryl or heteroaryl chlorides with aryllithium compounds catalyzed by nickel pincer complexes was performed under mild reaction conditions to afford biaryls in 23â 96â % yields.