Total Syntheses of (+)-Hyperbeanols A–C, (+)-Hyperpatulol A, and (−)-Hypercohone G, as Well as Structure Revision of Hyperpatulol A, and Hyperbeanol B

Hyperbeanols A-C, hyperpatulol A, and hypercohone G belong to spirocyclic polycyclic polyprenylated acylphloroglucinols (PPAPs). These natural products share the same unusual 6/6/5 spirocyclic skeleton and possess five stereocenters. The total syntheses of hyperbeanols A-C, hyperpatulol A, and hypercohone G have been accomplished. Among them, hyperbeanols B/C, hyperpatulol A, and hypercohone G were synthesized for the first time. The concise synthesis featured a Knoevenagel condensation to link two fragments and a Mn-(III)-mediated radical cyclization to construct the 6/6/5 spirocyclic skeleton. Besides, we also revised the structures of hyperpatulol A and hyperbeanol B.