Ni-Catalyzed Regioselective beta,delta-Diarylation of Unactivated Olefins in Ketimines via Ligand-Enabled Contraction of Transient Nickellacycles: Rapid Access to Remotely Diarylated Ketones

We disclose a [(PhO)(3)P]/NiBr2-catalyzed regioselective beta,delta-diarylation of unactivated olefins in ketimines with aryl halides and arylzinc reagents. This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H+ workup, diversely substituted beta,delta-diarylketones that are otherwise difficult to access readily with existing methods. Deuterium labeling and crossover experiments indicate that diarylation proceeds by ligand-enabled contraction of transient nickellacycles.