NiH-catalyzed asymmetric hydroalkynylation of α,β-unsaturated amides

An enantioselective NiH-catalyzed hydroalkynylation of α,β -unsaturated amides is reported. A wide range of α,β -unsaturated amides and bromoalkynes are suitable substrates for this reaction, which proceeds under mild conditions, allowing access to a variety of enantioenriched chiral β -alkynyl amides. β,γ -Unsaturated amides can also be used as substrates and undergo the β -selective hydroalkynylation with a slightly lower enantiomeric excess. A regio-reversed and enantiodifferentiating syn -hydrometalation of α,β -unsaturated amides with nickel hydride, followed by a subsequent stereospecific cross-coupling with bromoalkynes, is a convenient approach to the synthesis of enantioenriched chiral β -alkynyl amides.