Total Synthesis of the Phenolic Steroid Myrmenaphthol A.

Myrmenaphthol A is a structurally unique phenolic steroid with a naphthyl AB-ring system and an unusual C2 hydroxy group. Herein, we report the first total synthesis of this natural product in 10 steps from inexpensive, commercially available sitolactone. Key features of the synthesis include a Baran decarboxylative coupling and a Friedel-Crafts cyclization/olefin isomerization/aromatization cascade that rapidly assembled the tetracyclic core framework. This synthetic strategy is expected to be readily amenable to the synthesis of other phenolic steroids.