Enantioselective Synthesis of Skipped Dienes via Iridium-Catalyzed Allylic Alkylation of Phosphonates

An enantioselective synthesis of skipped dienes has been developed based on an iridium-catalyzed allylic alkylation of phosphonates and Horner-Wadsworth-Emmons olefination. This two-step protocol uses easily accessible substrates and delivers C2 -substituted skipped dienes bearing a C3 stereogenic center, generally with outstanding enantioselectivities (up to 99.5:0.5 er). This is the first catalytic enantioselective allylic alkylation of phosphonates, and the overall process represents a formal enantioselective alpha-C(sp2)-H allylic alkylation of alpha,beta-unsaturated carbonyls and acrylonitrile.