The Ni-catalyzed carboacylation of alkynes with amide electrophiles and triarylboroxines is presented. The reaction generates all-carbon tetrasubstituted alkene products in up to 62% yield. NiCl2·glyme is used as an inexpensive precatalyst in the absence of any external reductant or exogenous ligand. Design of Experiment (DoE) was used to achieve the best combination of yield and stereoselectivity in this acylative carbodifunctionalization of alkynes to generate highly substituted enones.

The enantioselective hydroarylation of vinylarenes catalyzed by a chiral, non-racemic nickel catalyst is presented as a facile method to generate chiral 1,1-diarylethanes. These reactions proceed via formation of a chiral, non-racemic nickel benzyl intermediate. Transmetalation with arylboron nucleophiles and subsequent reductive elimination enable the formation of a variety of chiral 1,1-diarylethanes. The 1,1-diarylethane products from reactions of arylboronic acids containing electron-donating substituents are formed with typically greater than 90% ee, while the 1,1-diarylethanes generated from reactions of arylboronic acids containing electron-withdrawing groups are generated with typically less than 80% ee. These results are consistent with the rate of transmetalation with an arylboron nucleophile playing a key role in the enantioselectivity of these hydroarylation reactions. This mechanistic insight has led to the development of reactions of neo-pentylglycolate esters of arylboronic acids with vinylarenes that occur with higher enantioselectivities based on increased rates of transmetalation.