Concise Total Synthesis of Peyssonnoside A

Peyssonnoside A is
a marine-derived sulfated diterpenoid glucoside
with a unique 5/6/3/6 tetracyclic skeleton with a highly substituted
cyclopropane ring deeply embedded into the structure. Herein, we report
the first total synthesis of this natural product in a concise, efficient,
scalable, and highly diastereoselective fashion. The aglucone peyssonnosol
was synthesized in 21% overall yield after 15 steps, featuring a Simmons–Smith
cyclopropanation and Mukaiyama hydration, fully controlled by the
spatial structure of the substrates.