Programmed Oxidation-Guided Divergent Total Syntheses of (±)-Anisatin, (±)-Neoanisatin, (±)-Majusanols A and B

The synthesis of complex, highly oxidized terpenes remains a central challenge, particularly when oxidation state dictates skeletal architecture. We establish a programmed oxidation strategy that prioritizes oxygen installation by its role in skeletal construction. This logic enabled the first total syntheses of neoanisatin (20 steps), majusanol A (18 steps), and majusanol B (19 steps), and delivered a significantly shorter route to anisatin (20 steps vs prior 40- and 43-step syntheses). Our work provides a generalizable design principle for the efficient and divergent synthesis of skeletally diverse, densely oxidized molecules.