Catalytic Asymmetric Total Synthesis of ent‐Hyperforin

Key to success: The first catalytic asymmetric total synthesis of ent-hyperforin (see picture) was accomplished by using a Diels–Alder reaction promoted by a chiral cationic iron catalyst (A; 96 % ee, d.r.>33:1), a diastereoselective Claisen rearrangement (B; 12:1 selectivity), an intramolecular aldol reaction (C), and a vinylogous Pummerer rearrangement (D) as key steps.