Total Syntheses of Highly Oxidized ent-Kaurenoids Pharicin A, Pharicinin B, 7‑O‑Acetylpseurata C, and Pseurata C: A [5+2] Cascade Approach

The unprecedented oxidative dearomatization-induced [5+2] cycloaddition/pinacol-type 1,2-acyl migration cascade efficiently generates a quaternary carbon center and assembles the highly oxygenated bicyclo[3.2.1]­octane framework of ent-kaurene diterpenoids. By incorporation of the subsequent retro-aldol/aldol process and singlet oxygen ene reaction, this concise and convergent approach has enabled the first asymmetric total syntheses of pharicin A, pharicinin B, 7-O-acetylpseurata C, and pseurata C.