Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education and Yunnan province, State Key Laboratory for, Conservation and Utilization of Bio-Resources in Yunnan, School of, Chemical Science and Technology, Yunnan University, Kunming, Yunnan, 650091, P. R. China.
Chemistry. 2019 Feb 26;25(12):3005-3009. doi: 10.1002/chem.201806411. Epub 2019 Jan 29.
Cyclodipeptide 2,5-diketopiperazines (DKP) are privileged structural units present in drugs and natural alkaloids. This work reports a new method for the synthesis of biologically important DKP scaffolds based on an intramolecular nucleophilic α-addition of general amides towards an alkynamide system. The utility of this umpolung cyclization mediated by trimethyl phosphine and l-glutamic acid is highlighted by its application to the concise total syntheses of 6-methoxyspirotryprostatin B (the first total synthesis), spirotryprostatin A, and spirotryprostatin B.
环二肽 2,5-二酮哌嗪（DKP）是存在于药物和天然生物碱中的重要结构单元。本工作报道了一种基于一般酰胺对炔酰胺体系的分子内亲核 α-加成反应合成具有生物重要性的 DKP 支架的新方法。三甲基膦和 L-谷氨酸介导的这种反转环化反应的实用性通过其在 6-甲氧基螺普罗托菌素 B（首次全合成）、螺普罗托菌素 A 和螺普罗托菌素 B 的简洁全合成中的应用得到了强调。
