A general catalytic oxo-hetero-Diels−Alder reaction for pro-chiral aldehyde and ketone N-oxy-pyridinesis presented. The catalytic and asymmetric oxo-hetero-Diels−Alder reaction of electron-rich dienes withN-oxy-pyridine-2-carbaldehyde and ketone derivatives, catalyzed by chiral copper(II)−bisoxazolinecomplexes, gives optically active six-membered oxygen heterocycles in moderate to good yields andwith excellent enantioselectivities.