π-Facial diastereoselectivity in the electrophilic and electrophilic–nucleophilic additions to dimethyl (1R,2R,3S,4S)-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate

Abstract

The π-facial selectivity of attack of electrophilic species (OsO₄, m-ClC₆H₄CO₃H, BH₃) on the sterically unbiased dimethyl (1 R,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 Cleplak transition state theory.