Synthesis and Absolute Configuration of the Bacterial cis-1,2-, cis-8,9-, and cis-10,11-Dihydrodiol Metabolites of Benzanthracene Formed by a Strain of Beijerinckia

Article abstract of DOI:10.1021/jo00193a033

Metabolism of the environmental contaminant benzanthracene has been examined with the bacterium Beijerinckia B8/36.This organism is a mutant strain of the wild type, which lacks the ability to oxidize further initially formed cis-dihydrodiol metabolites of aromatic hydrocarbons.The main isolated metabolites of benzanthracene consist of the cis-1,2-, cis-8,9-, and cis-10,11-dihydrodiols in a ratio of 73:15:12, respectively.Synthesis of the dihydrodiols in optically pure form from precursors whose configurations were previously known or have been assigned in thepresent study has established that the metabolites are of very high enantiomeric purity and have 1R,2S, 8R,9S, and 10S,11R absolute configurations.In the course of these assignments, the (+)-isomer of 1,2-epoxy-1,2,3,4-tetrahydrobenzanthracene has been established to have 1R,2S absolute configuration, and a prior assignment of (-)-trans-(1R,2R)-1,2-dihydroxy-1,2-dihydrobenzanthracene has been confirmed.The chemical interrelationships of absolute configuration have been done in such a manner that the cis-1,2-, cis-8,9-, and cis-10,11-dihydrodiols formed by the bacterium are tied directly to structures which have been used to assign the corresponding trans-1,2-, trans-8,9-, and trans-10,11-dihydrodiols formed from benzanthracene in mammalian liver.