Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Departments of Pharmacology and Therapeutic Radiology, Yale School of Medicine, New Haven, Connecticut 06520, United States.
Org Lett. 2023 May 26;25(20):3723-3727. doi: 10.1021/acs.orglett.3c01175. Epub 2023 May 12.
Here, we report an enantioselective synthesis of the monomeric product (-)-nenestatin A, via the intermediary diazofluorene "diazonenestatin A." Our route features a convergent, aldol-based fragment coupling to assemble the carbon skeleton and a diazotransfer to a highly conjugated tetracyclic fulvene. We find that diazonenestatin A is transformed to nenestatin A under conditions that mimic the bacterial fermentation, suggesting that the pathway may produce unstable diazofluorene products that have eluded isolation.
在这里,我们通过中间体重氮氟蒽“重氮那替丁 A”报道了单体产物(-)-那替丁 A 的对映选择性合成。我们的路线具有收敛的,基于烯醇缩合的片段偶联来组装碳骨架和重氮转移到高度共轭的四环富烯。我们发现,在模拟细菌发酵的条件下,重氮那替丁 A 转化为那替丁 A,这表明该途径可能产生不稳定的重氮氟蒽产物,这些产物难以分离。