Rao Peirong, Tang Dongmin, Xia Qidong, Hu Jialei, Lin Xufeng, Xuan Jun, Ding Hanfeng
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Am Chem Soc. 2025 Jan 29;147(4):3003-3009. doi: 10.1021/jacs.4c16265. Epub 2025 Jan 8.
The asymmetric and divergent total syntheses of two phragmalin (moluccensins G and H) and two khayanolide-type (krishnolide F and khayseneganin F) limonoids were disclosed, which employed a torquoselective interrupted Nazarov cyclization as the key step. Taken together with a Liebeskind-Srogl coupling, a benzoin condensation, and bidirectional acyloin rearrangements, our strategy would simplify the synthetic design of both phragmalin and khayanolide-type limonoids and facilitate their modular syntheses. Moreover, the described approach also provides additional insights into the biosynthetic relationships between these two distinct skeletons.
报道了两种苦木素（莫卢辛素G和H）和两种卡扬内酯型（克里什诺利德F和卡扬塞加宁F）柠檬苦素的不对称和发散性全合成，该合成以扭转选择性中断的纳扎罗夫环化反应作为关键步骤。结合利伯斯金德-施罗格偶联反应、安息香缩合反应和双向偶姻重排反应，我们的策略将简化苦木素和卡扬内酯型柠檬苦素的合成设计，并促进它们的模块化合成。此外，所描述的方法还为这两种不同骨架之间的生物合成关系提供了更多见解。
