Zinc(II)-Catalyzed Asymmetric Diels-Alder Reaction of (E)-1-Phenyl Dienes with β,γ-Unsaturated α-Ketoesters

A highly regio-, diastereo-, and enantioselective Diels-Alder reaction of beta,gamma-unsaturated alpha-ketoesters with (E)-1-phenyl dienes has been accomplished by using a stable and easily available chiral N,N'-dioxide/zinc(II) complex as catalyst. Only one isomer of the corresponding cyclohexenes with three chiral centers was obtained in good to excellent yields with excellent ee values under mild reaction conditions. The configurations of the product and chiral N,N'-dioxide/zinc(II) catalyst were identified by X-ray diffraction analysis. In addition, a possible catalytic model was proposed to explain the origin of the asymmetric induction.