Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
Org Lett. 2022 Sep 16;24(36):6499-6504. doi: 10.1021/acs.orglett.2c02272. Epub 2022 Aug 9.
A stereoselective synthetic entry point to the 5-8-5 carbocyclic core of the ophiobolins was developed. This strategy exploits the chiral tertiary alcohol of ophiobolin A to guide assmebly of the 5-8-5 scaffold in a single step via a photoinitiated cycloisomerization. Mechanistic insights into the origin of stereocontrol in this reaction are described, as are efforts to elaborate the resultant fused 5-8-5 ring system to the pharmacophore of ophiobolin A.
开发了一种对ophiobolins 的 5-8-5 碳环核心具有立体选择性的合成切入点。该策略利用 ophiobolin A 的手性叔醇，通过光引发的环异构化，在一步反应中引导 5-8-5 支架的组装。描述了该反应中立体控制起源的机理见解，以及努力阐述所得的稠合 5-8-5 环系统到ophiobolin A 的药效团。
