Unexpected Diels–Alder/Carbonyl-ene Cascade toward the Biomimetic Synthesis of Chloropupukeananin

The biomimetic synthesis of the advanced model compound of chloropupukeananin has been achieved. The present synthesis features an unexpected enantiomer-differentiating Diels–Alder/carbonyl-ene cascade under high-pressure conditions and a base-promoted migration of the salicyl group.