Theunissen Cédric, Métayer Benoît, Lecomte Morgan, Henry Nicolas, Chan Hwai-Chien, Compain Guillaume, Gérard Phidéline, Bachmann Christian, Mokhtari Naima, Marrot Jérome, Martin-Mingot Agnès, Thibaudeau Sébastien, Evano Gwilherm
Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, 1050 Brussels, Belgium.
Org Biomol Chem. 2017 May 23;15(20):4399-4416. doi: 10.1039/c7ob00850c.
Polycyclization reactions are among the most efficient synthetic tools for the synthesis of complex, polycyclic molecules in a single operation from simple starting materials. We report in this manuscript a full account on the discovery and development of a novel cationic polycyclization from readily available ynamides. Simple activation of these building blocks under acidic conditions enables the generation of highly reactive activated keteniminium ions, which triggers an unprecedented cationic polycyclization yielding highly substituted polycyclic nitrogen heterocycles possessing up to seven fused cycles and three contiguous stereocenters.
多环化反应是从简单起始原料通过单一操作合成复杂多环分子最有效的合成工具之一。在本手稿中，我们全面报道了一种由易于获得的烯酰胺进行新型阳离子多环化反应的发现和发展。在酸性条件下简单活化这些结构单元能够生成高反应活性的活化酮亚胺离子，从而引发前所未有的阳离子多环化反应，生成具有多达七个稠合环和三个相邻立体中心的高度取代的多环氮杂环化合物。
