The highly stereoselective intermolecular all-carbon [4+2] annulation between in situ generated acyclic dienolates and α,β-unsaturated acyl azoliums is disclosed. The identification of 2-acyloxy-3-butenones as suitable diene precursors is the key to the success of this transformation. The corresponding highly functionalized cyclohexene products, which are inaccessible from Diels-Alder reactions, were delivered with high levels of diastereo- and enantioselectivities. A series of further transformations based on the product showed the potential of this reaction.