Synthesis of the Enantiomeric K-Region Arene 5,6-Oxides Derived from Chrysene, 7,12-Dimethylbenzanthracene, and Benzophenanthrene

Article abstract of DOI:10.1021/jo00377a025

K-region arene 5,6-oxides of chrysene, benzophenanthrene Ph>, and 7,12-dimethylbenzanthracene (DMBA) have been synthesized from resolved cis-5,6-dihydrodiols by the ortho ester route as well as from separated bromo(menthyloxy)acetate precursors in the cases of chrysene and BPh.Absolute configurations of the 5,6-oxides and their precursors from chrysene and DMBA have been determined by nucleophilic trans addition of methanol to the oxirane ring and correlation by circular dichroism of the adducts with trans dihydrodiols of known configurations.Confirmation of the configurational assigments to the enantiomeric chrysene cis-5,6-dihydrodiols was achieved by reduction to cis-5,6-dihydroxy-1,2,3,4,5,6-hexahydrochrysene and determination of the skew sense of the resulting biphenyl chromophore through CD measurements.BPh 5,6-oxide enantiomers were assigned by direct comparision with a sample of known configuration on a chiral column.