Two efficient new chiral copper (II) Schiff base complexes were developed for the highly enantio- and diastereoselective HDA reaction of Brassard type diene 1b with aldehydes, to afford the corresponding 5-methyl-containing alpha,beta-unsaturated delta-lactone derivatives in moderate yields, high enantioselectivities (up to 99% ee) and excellent diastereoselectivities (up to 99:1 anti/syn). On the basis of the absolute configuration of 4a-4j disclosed by X-ray diffraction and CD analysis, a possible transition-state model for the enantio- and diastereoselective catalytic reaction has been proposed.