Jun Huang,* Tingting Cao, Zhongchao Zhang, and Zhen Yang*
J. Am. Chem. Soc. 2022, 144,(6)
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.![](/__local/A/4B/DE/127C552CD0F3F8C7F7D7CA6DD20_12E91830_154BF.jpeg?e=.jpeg)