Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides

A nickel-catalyzed conjunctive cross-coupling
of simple alkenyl
amides with aryl iodides and aryl boronic esters is reported. The
reaction is enabled by an electron-deficient olefin (EDO) ligand,
dimethyl fumarate, and delivers the desired 1,2-diarylated products
with excellent regiocontrol. Under optimized conditions, a wide range
of amides derived from 3-butenoic acid, 4-pentenoic acid, and allyl
amine are compatible substrates. This method represents the first
example of regiocontrolled 1,2-diarylation directed by a native amide
functional group. Computational analysis sheds light on the potential
substrate binding mode and the role of the EDO ligand in the reductive
elimination step.