BACTERIAL DIOXYGENASE-CATALYZED DIHYDROXYLATION AND CHEMICAL RESOLUTION ROUTES TO ENANTIOPURE CIS-DIHYDRODIOLS OF CHRYSENE

Biotransformation of the environmental pollutant chrysene 1 by resting cells of a mutant strain (B8/36) of the soil bacterium Sphingomonas y anoikuyae produces (+)-cis-3,4-dihydroxy-3,4-dihydrochrysene 4 which h as been assigned (3S,4R) absolute configuration by stereochemical corr elation with 3S,4R)cis-3,4-dihydroxy-1,2,3,4-tetrahydrochrysene 6. Bot h cis-3,4-diol 6 and cis-1,2-dihydroxy-1,2,3,4-tetrahydrochrysene 12 a re obtained in enantiopure form after chromatographic separation of th e individual ethoxy-2-phenyl-2-trifluoromethylacetyl)(bis-MTPA) diaste reoisomers of compound 6 and the MTPA diastereoisomers of bromohydrin 19, respectively, followed by hydrolysis. A new general synthetic rout e to cis-dihydrodiols, from the corresponding cis-tetrahydrodiol cycli c carbonates, is used to obtain both racemic and enantiopure forms of the bay-region diol 4, and the non-bay region diol 5. H-1 NMR and CD s pectra of the cis- and trans-dihydrodiols of chrysene are described.