The asymmetric dihydroxylation procedure (AD) is applied to a variety of polyenes. In many cases excellent regioselectivities are obtained. The observed selectivities are rationalized in terms of electronic and/or steric effects inherent to the substrate, superimposed on the substrate's favorable or unfavorable interactions with the binding pocket of the AD ligand. Surprisingly, for medium and large ring olefins with trans-double bonds outstanding enantioselectivities are realized using the pyrimidine ligands. A hexaol of D 3 symmetry is prepared from all trans cyclododecatriene.