Total Syntheses of (±)-Acetoxymarsupellone and (±)-Marsupellins A, B, and D Enabled by a Reductive Cyclization and Semipinacol Rearrangement Strategy

作者：Jiuzhou Yi, Min He, Yan Zhang, Pengfei Yu, Xingang Xie, Huilin Li, Xuegong She · 发表于：Organic Letters · 年份：2024 · DOI：10.1021/acs.orglett.4c01572 · 被引用次数：6 · 研究领域：Cancer Treatment and Pharmacology、Synthetic Organic Chemistry Methods、Asymmetric Synthesis and Catalysis

We report herein the total syntheses of three marsupellin-family sesquiterpenoids, (±)-acetoxymarsupellone and (±)-marsupellins B and D, in 14–19 steps from our known precursor, making marsupellin A also accessible from marsupellin B through a known procedure. The critical tricyclic framework bearing the challenging C7 bridgehead all-carbon quaternary center is strategically constructed through a Ti-mediated reductive cyclization and semipinacol rearrangement sequence. This study provides a general approach to the syntheses of ( ent -)longipinane-type molecules.