Ni-Catalyzed Three-Component Alkene Carboacylation Initiated by Amide C-N Bond Activation

The nickel-catalyzed intermolecular carboacylation of alkenes with amides and tetraarylborates is presented. Bicyclic alkenes are readily functionalized with a variety of N-benzoyl-N-phenylbenzamides and triarylboranes, which are generated in situ from the corresponding tetraarylborates, to synthesize ketone products in up to 91% yield. Preliminary mechanistic studies suggest that migratory insertion precedes transmetalation and that reductive elimination is the turnover-limiting step. These reactions occur with excellent chemoselectivity and diastereoselectivity in the absence of a directing/chelating group and further demonstrate amides as practical acyl electrophiles for alkene dicarbofunctionalization reactions.