Iridium-Catalyzed Enantioselective α-Allylic Alkylation of Amides Using Vinyl Azide as Amide Enolate Surrogate.

Among the unstabilized enolates used as nucleophiles in iridium-catalyzed asymmetric allylic alkylation reactions, amide enolates are the least explored. Vinyl azides are now employed as amide enolate surrogates in Ir-catalyzed asymmetric allylic alkylation with branched allylic alcohols as the allylic electrophile. Competing reaction pathways are suppressed through the systematic tuning of the steric and electronic properties of vinyl azide to effect the α-allylic alkylation of secondary acetamides with high atom economy, exclusive branched selectivity, and mostly excellent enantioselectivity.