Herein, we describe the first total synthesis of (+)-ent-vetiverianine A, which exhibits a 5/6/6-fused tricyclic structure. The key reactions, including Lewis acid-mediated cyclization, Mukaiyama hydration, enantioselective Shi epoxidation, Birch reduction,...

In this article, we report the synthesis of (±)-5-epi-vetiverianine A. The key reactions, including a rhodium-catalyzed coupling reaction and an oxidative phenolic cyclization, allow for efficient and stereoselective access to (±)-5-epi-vetiverianine A with 11 steps, and in 20% overall yield. Stereochemistry was confirmed by the NOE study.