The Asymmetric Olefinative Conjugate Addition

The asymmetric olefinative conjugate addition (AOCA) is presented, which involves an enantioselective conjugate addition to an olefin activated by a traceless electron-withdrawing group, which then allows for an olefinative quench with a carbonyl com-pound. This approach is demonstrated by the Cu-catalyzed enantioselective conjugate addition of organoboron and organozinc reagents to an alkenyl phosphonate, followed by quenching with a carbonyl compound to yield the corresponding alkene via Horner-Wadsworth-Emmons olefination. This one-pot sequence efficiently produces chiral internal olefins, addressing a common limitation of Cu-catalyzed enantioselective allylic substitutions, which typically only generate terminal alkenes. The versatility of this strategy is showcased through the synthesis of various structurally diverse products with high yields, complete diastereocon-trol, and enantiomeric ratios of up to 98:2.