Methanol-Mediated Nickel-Catalyzed Chemo- and Enantioselective Three-Component Alkenylative Coupling of Aldimines and Alkynes with Alkenyl Boronic Acids

1,3-Dienyl amines are important and versatile motifs in organic synthesis, and the functionalization of π-components with aldimines has emerged as a powerful strategy for their construction. However, existing methods typically rely on conjugated enynes or dienes and are limited to two-component reactions. Herein, we report a nickel-catalyzed chemoselective three-component alkenylative coupling of aldimines, simple alkynes, and alkenyl boronic acids, which provides stereodefined, multisubstituted 1,3-dienyl amines in good to excellent yields (up to 97% yield). Methanol acts as a sustainable protic solvent, facilitating the ring opening of the aza-nickelacycle intermediate generated via oxidative cyclization of the aldimine and alkyne. Furthermore, employing a <i>P</i>-chiral monophosphine ligand allows the enantioselective variant of this reaction to proceed with excellent stereocontrol (up to 98% yield and 99% ee).