Centre for Analysis and Synthesis, Department of Chemistry, Lund University, Box 124, SE-221 00 Lund, Sweden.
J Am Chem Soc. 2021 Dec 22;143(50):21218-21222. doi: 10.1021/jacs.1c10364. Epub 2021 Nov 22.
Asymmetric construction of dithiodiketopiperazines on otherwise achiral scaffolds remains a pivotal synthetic challenge encountered in many biologically significant natural products. Herein, we report the first total syntheses of (-)-glionitrin A/B and revise the absolute configurations. Emerging from the study is a novel oxidative sulfenylation of triketopiperazines that enables asymmetric formation of dithiodiketopiperazines on sensitive substrates. The concise route paves the way for further studies on the potent antimicrobial and antitumor activities of glionitrin A and the intriguing ability of glionitrin B to inhibit invasive ability of cancer cells.
在手性骨架上不对称构建二硫二酮哌嗪仍然是许多具有重要生物学意义的天然产物中遇到的关键合成挑战。在此，我们报告了 (-)-glionitrin A/B 的首次全合成，并修正了它们的绝对构型。研究中还出现了一种新的三酮哌嗪的氧化亚磺化反应，可在敏感底物上不对称形成二硫二酮哌嗪。这条简洁的路线为进一步研究 glionitrin A 的强大抗菌和抗肿瘤活性以及 glionitrin B 抑制癌细胞侵袭能力的有趣能力铺平了道路。
