Synthesis and thermal racemization of the predominant arene oxide metabolite of chrysene, (+)-(3S,4R)-chrysene 3,4-oxide

Abstract

(–)-trans-4-Bromo-3-hydroxy-1,2,3,4-tetrahydrochrysene has been obtained from the chromatographic separation and cleavage of the corresponding menthyloxyacetyl (MOA) diastereoisomer. The (–)-enantiomer of this bromohydrin has been assigned (3R,4R)absolute stereochemistry and used in the synthesis of (+)-(3S,4R)-chrysene 3,4-oxide. Thermal racemization studies on this arene oxide gave a barrier to racemization (E_a) of 25.15 kcal mol^–1 and an activation entropy (ΔS^‡) of 0.7 cal mol^–1 K^–1, in accord with PMO predictions.