Nickel-Catalyzed Benzylic Alkynylation: Migratory Hydroalkynylation and Enantioselective Hydroalkynylation of Olefins with Bromoalkynes

A nickel-hydride catalyzed reductive migratory hydroalkynylation of olefins with bromoalkynes that delivers the corresponding benzylic alkynylation products in high yield and with excellent regioselectivity has been developed. Catalytic enantioselective hydroalkynylation of styrenes has been realized using a simple chiral PyrOx ligand. The obtained enantioenriched benzylic alkynes are versatile synthetic intermediates and can be readily transformed into synthetically useful chiral synthons