Highly Enantioselective Synthesis of Propargyl Amide with Vicinal Stereocenters through Ir‐Catalyzed Hydroalkynylation

Chiral propargyl amines are valuable synthetic intermediates for the preparation of biologically active compounds and functionalized amines. Catalytic methods to access propargyl amines containing vicinal stereocenters with high diastereoselectivity are particularly rare. We report an unprecedented strategy for the synthesis of enantioenriched propargyl amines with two stereogenic centres. An iridium complex, ligated by a phosphoramidite ligand, catalyzes the hydroalkynylation of β,β‐disubstituted enamides to afford propargyl amides in a highly regio‐, diastereo‐, and enantioselective fashion. Stereodivergent synthesis of all four possible stereoisomers was achieved using this strategy.