Synthesis and Desymmetrization of meso Tricyclic Systems Derived from Benzene Oxide

Ozonolysis of the Diels-Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully substituted, meso bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH₄. Variation in the workup allowed for isolation of two different diastereoisomers, through double epimerization of the imide stereocenters. Desymmetrization of the resulting meso diols via asymmetric nucleophilic epoxide opening and acylation reactions provided access to highly substituted, enantioenriched fused rings.