Total Synthesis of ent-Dioxepandehydrothyrsiferol via a Bromonium-Initiated Epoxide-Opening Cascade

Journal of the American Chemical Society 131(34), 12084-12085, DOI: 10.1021/ja9052366

In the first total synthesis of ent-dioxepandehydrothyrsiferol, the signature trans-anti-trans 7,7,6-fused tricyclic polyether framework was constructed in a single bromonium-initiated epoxide-opening cascade that incorporates both endo- and exo-selective epoxide openings, each directed by the substitution pattern of the epoxide (methyl groups). This study thus demonstrates the feasibility of a possible biogenesis.