The pi-facial selectivity of attack of electrophilic species (OsO4, m-ClC6H4CO3H, BH3) on the sterically unbiased dimethyl (1R,2R,3S,4S)-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate is controlled syn to the exo electron-withdrawing ester substituents, and the reactions of phenylselenyl chloride and phenylsulfenyl chloride show opposing diastereoselectivities, which can be explained using the Cieplak transition state theory.