163.Semisynthesis of (−)-Bufospirostenin A Enabled by Photosantonin Rearrangement Reaction

Jun Huang,* Tingting Cao, Zhongchao Zhang, and Zhen Yang*

J. Am. Chem. Soc. 2022, 144,(6), 2479–2483

An enantioselective semisynthesis of (−)-bufospirostenin A is described. The key steps in the synthesis involve use of our proposed biomimetic and diastereoselective photosantonin rearrangement reaction for construction of the 5/7 bicyclic motif, and a Co-catalyzed reversible double-bond isomerization reaction for installing the double bond in the seven-membered ring.