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Updated: Jan 31, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Total Synthesis of Spirotryprostatins through Organomediated Intramolecular Umpolung Cyclization
Yong-Kai Xi1, Hongbin Zhang1, Rui-Xi Li1
1Key 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.
Abstract:
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.
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