[formula: see text] Highly stereoselective formal [3 + 3] cycloaddition reactions of chiral vinylogous amides with alpha, beta-unsaturated iminiums are described. A mechanistic model is proposed to rationalize the observed stereoselectivity. The 6 pi-electron electrocyclic ring closure appears to be reversible, and a preferred rotation of the alkenyl group, one of the three 2 pi-components, during the ring closure step provides the thermodynamically favored diastereomer as the major product.