Asymmetric Total Synthesis of Bufospirostenin A

作者：Min-Jing Cheng, Liping Zhong, Chen‐Chen Gu, Xujiang Zhu, Bo Chen, Junshan Liu, Lei Wang, Wen‐Cai Ye, Chuang‐Chuang Li · 发表于：Journal of the American Chemical Society · 年份：2020 · DOI：10.1021/jacs.0c05479 · 被引用次数：46 · 研究领域：Marine Sponges and Natural Products、Synthetic Organic Chemistry Methods、Microbial Natural Products and Biosynthesis

The first and asymmetric total synthesis of bioactive bufospirostenin A, an unusual spirostanol with rearranged A/B rings, was accomplished. The synthetically challenging [5-7-6-5] tetracyclic ring system, found in bufospirostenin A and some other natural products, was efficiently constructed by the unique intramolecular rhodium-catalyzed Pauson-Khand reaction of an alkoxyallene-yne. The 11 stereocenters in the final product, including the 10 contiguous stereocenters, were installed diastereoselectively.