Face-selectivity in [4+2]-cycloadditions to novel polycyclic benzoquinones. Remarkable stereodirecting effects of a remote cyclopropane ring and an olefinic bond

π-Face selectivity in Diels–Alder reactions between specially crafted bicyclo[2.2.2]octane-fused benzoquinones, where the dienophilic moiety is imbedded in an isosteric environment, can be modulated by a remote olefinic bond and a cyclopropane ring. Quantum mechanical calculations while reproducing the observed diastereoselectivities at the TS level indicate the involvement of ground state orbital effects.