Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Abstract

AbstractCatalytic enantioselective functionalization of unactivated 1,1‐disubstituted alkenes is challenging due to the difficulty to discriminate the enantiotopic faces. Enantioselective hydrofunctionalization of unactivated 1,1‐disubstituted alkenes with tunable Markovnikov and anti‐Markovnikov selectivity remains elusive. We report here an amide‐directed, regiodivergent and enantioselective hydroalkynylation of unactivated alkenes. The regioselectivity can be readily tuned by the choice of a proper ligand. Catalytic alkynylations occurred with tunable Markovnikov and anti‐Markovnikov selectivity to afford products containing acyclic tertiary or quaternary stereocenters β to an amide. Combining a sequence of alkene isomerization and regioselective hydroalkynylation, we further realized an iridium‐catalyzed formal asymmetric conjugated alkynylation of β,β‐disubstituted α,β‐unsaturated amides. Computational studies suggest that the regioselectivity is dictated by the ligand structures.