Synthesis of higher oxidized metabolites of dibenz(a,j)anthracene implicated in the mechanism of carcinogenesis

The unsymmetrical 3,4,8,9-bis(dihydrodiol) and the 10- and 11-phenolic trans-3,4- dihydrodiols of dibenz(a,j)anthracene were efficiently synthesized. The synthetic approach involves as key steps the asymmetric dihydroxylation of a stilbene precursor using a Sharpless catalyst and intramolecular cyclodehydrobromination catalyzed by Pd(PPh3)2Cl2. Good yields were obtained in all 13 steps of the synthesis of 3,4,8,9-bis(dihydrodiol) except one, with the overall yield placed at 17%.