Certain cyclic sulfates (e.g. 23) together with various of their precursor sulfites (e.g. 21 and 22) have been prepared from the corresponding chiral, non-racemic bicyclo[2.2.2]octane-2,3-diols (e.g. 20). Such diols are obtained by engaging the corresponding enzymatically derived and enantiomerically enriched or homochiral cis-1,2-dihydrocatechol (e.g. 10) or certain derivatives in either inter- or intra-molecular Diels–Alder cycloaddition reactions. Other functionalities present within the title compounds can be chemoselectively manipulated without adversely affecting the associated sulfate residues.