Enantioselective Synthesis of Habiterpenol and Dasyscyphin A

Meroterpenoid natural products exhibit remarkable structural diversity and biological activity but often present formidable stereochemical challenges in total synthesis. Recently, we reported the enantioselective total synthesis of habiterpenol and dasyscyphin A, two meroterpenoids bearing synthetically demanding cis-hydrindane frameworks. By combining Ti-catalyzed radical polyolefin cyclization with photocatalytic epimerization of ketone-adjacent quaternary stereocenters, our three-phase biomimetic strategy overrides the intrinsic preference of polyolefin cyclizations for all-trans-fused products. These studies demonstrate how post-cyclization stereochemical remodeling can expand the accessible outcomes of biomimetic polyolefin cyclizations.