The direct Ir-catalyzed cross-coupling between branched, racemic allylic alcohols and simple olefins is described. This transformation is catalyzed by an Ir–(P, olefin) complex and proceeds with high site selectivity and excellent enantioselectivity. The method allows rapid access to various 1, 5-dienes or trienes and was used in the catalytic asymmetric synthesis of the γ-secretase modulator JNJ-40418677.