Nickel-Catalyzed Asymmetric Hydroalkynylation of 1,3-Dienes

Significance

Catalytic conversion of alkyne C-H bonds through C-C bond formation without the stoichiometric generation of acetylides is a desirable atom-economical process. The catalytic ­hydroalkynylation (addition of alkyne C-H bonds across unactivated C-C multiple bonds) has gained significant attention, but the asymmetric version of such process has been limited to ­rhodium-catalyzed hydroalkynylation of allenes. The authors report a nickel-catalyzed asymmetric hydroalkynylation of 1-aryl-1,3-butadienes 2 with a terminal alkyne 1 that contains an α-siloxy-sec-alkyl group, in the presence of a TADDOL-based chiral phosphoramidite ligand (R,R)-L.