Title: Enantioselective Total Synthesis of Bipolarolides A and B

Authors: Yufei Liu, Ke Sun, Qi Wei, Jin Chen, Shengling Sun, Yaxin Li, Zhongkai Feng, Yingying Guo, Zhaohong Lu*

Abstract: Bipolarolides A and B are members of the ophiobolin family of sesterterpenes, characterized by their intricate cage-like structures. Herein we report a concise asymmetric total synthesis of bipolarolides A and B enabled by the type-II Diels–Alder reaction. The synthesis features a sequence of key transformations: an iridium-catalyzed enantioselective allylation to establish the first stereocenter, type-II Diels–Alder reaction to rapidly assemble the bicyclo[3.3.1]non-1-ene core, reductive oxy-ring opening with olefin isomerization, aldol cyclization to construct a D ring, and a late-stage electrochemical C–H oxidation to complete the ether ring.

Full-Link: https://doi.org/10.1021/jacs.5c09835