Enantioselective Total Synthesis of (−)-Hamigeran F and Its Rearrangement Product

Herein, we report the first enantioselective total synthesis of the highly complex hamigeran diterpenoid (−)-hamigeran F and its rearrangement product. The synthetic strategy features key steps of asymmetric hydrogenation, Horner–Wadsworth–Emmons olefination, and intramolecular Friedel–Crafts acylation to construct the [6,6,5]-tricyclic skeleton bearing three consecutive stereocenters, a sequence of steps involving Rosenmund reduction, Wittig reaction, dihydroxylation to assemble the α-acetoxy ketone group, and an intramolecular aldol reaction to build the tetracyclic core structure.