Formal Synthesis of (+)‐Phomactin A via a Prins/Conia‐ene Cascade and γ‐Hydroxylation Strategy

Abstract An asymmetric formal synthesis of (+)‐phomactin A has been accomplished. The key steps in the synthetic strategy included establishing the AB ring system in one‐pot via Prins/Conia‐ene cascade cyclization reaction and the C ring formation via γ‐hydroxylation of enone in the late‐stage of the synthesis. The two major fragments are readily prepared from (+)‐pulegone and geraniol via a modified Eschenmoser–Tanabe fragmentation strategy in 6 steps and a Sharpless asymmetric epoxidation/hydrozirconation/ Roskamp reaction sequence in 11 steps respectively.