Synthesis of Amides with Remote Stereocenters by Catalytic Asymmetric γ-Alkynylation of α,β-Unsaturated Amides

Abstract

An iridium-catalyzed enantioselective hydroalkynylation of α,β-unsaturated amides was described. The selectivity of this reaction is distinct from that observed in many catalytic hydroalkynylations of α,β-unsaturated carbonyl compounds. It occurs selectively at the γ instead of the β position. Preliminary mechanistic studies suggest that the reaction proceeds through alkene isomerization followed by hydroalkynylation. This method provides a straightforward route for the synthesis of amides with a remote stereocenter at the γ position.