Iridium-Catalyzed Enantioselective Hydroalkynylation of Enamides for the Synthesis of Homopropargyl Amides

Reported is an iridium‐catalyzed asymmetric hydroalkynylation of enamides with terminal alkynes. The reaction occurs regioselectively at the β‐position of an enamide to produce homopropargyl amides. Good to high enantioselectivity was observed with an iridium complex ligated by a chiral bis(phosphine) ligand. This method provides a straightforward route to synthesize chiral homopropargyl amides with a stereocenter β to the amide. Jockeying into position: The title reaction proceeds regioselectively with reaction at the β‐position of an enamide, thus delivering homopropargyl amides. Good to high enantioselectivities were observed with an iridium complex ligated by the Ph‐BPE ligand. This method provides a straightforward route to the synthesis of chiral homopropargyl amides with a stereocenter β to the amide. cod=1,5‐cyclooctadiene, Tf=trifluoromethanesulfonyl.