The iridium-catalyzed enantioselective coupling reaction of vinyl azides and allylic electrophiles is presented and provides access to beta-chiral carbonyl derivatives. Vinyl azides are used as acetamide enolate or acetonitrile carbanion surrogates, leading to gamma, delta-unsaturated beta-substituted amides as well as nitriles with excellent enantiomeric excess. These products are readily transformed into chiral N-containing building blocks and pharmaceuticals. A mechanism is proposed to rationalize the chemoselectivity of this coupling reaction.