Transamidation of N-acyl-glutarimides with amines
Transamidation of N-acyl-glutarimides with amines
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N-酰基戊二酰亚胺与胺的转酰胺基化
DOI：
10.1039/c7ob02874a
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Szostak Michal
中科院分区：
文献类型：
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作者：
Liu Yongmei;Achtenhagen Marcel;Liu Ruzhang;Szostak Michal
由于酰胺键在化学的各个领域中的核心作用，用于合成酰胺的新的转酰胺基反应的发展是一个重要且活跃的研究领域。在此，我们报道了一种在温和、无金属条件下用胺与 N-酰基戊二酰亚胺进行转酰胺基化的新方法，该方法依赖于酰胺键扭曲来削弱酰胺共振。在反应条件下，可以耐受多种胺和官能团，包括在金属催化方案中可能出现问题的亲电子取代基。机理实验表明酰胺键扭曲、四面体中间体的热力学稳定性和戊二酰亚胺的离去基团能力是控制该过程反应性的因素。该方法进一步确立了 N-酰基戊二酰亚胺作为实验室稳定、扭曲垂直、基于酰胺的试剂在无金属途径的酰基转移反应中的合成用途。讨论并比较了无金属和金属催化过程中 N-酰基戊二酰亚胺的反应性起源。
The development of new transamidation reactions for the synthesis of amides is an important and active area of research due to the central role of amide linkage in various fields of chemistry. Herein, we report a new method for transamidation of N-acyl-glutarimides with amines under mild, metal-free conditions that relies on amide bond twist to weaken amidic resonance. A wide range of amines and functional groups, including electrophilic substituents that would be problematic in metal-catalyzed protocols, are tolerated under the reaction conditions. Mechanistic experiments implicate the amide bond twist, thermodynamic stability of the tetrahedral intermediate and leaving group ability of glutarimide as factors controlling the reactivity of this process. The method further establishes the synthetic utility of N-acyl-glutarimides as bench-stable, twist-perpendicular, amide-based reagents in acyl-transfer reactions by a metal-free pathway. The origin of reactivity of N-acyl-glutarimides in metal-free and metal-catalyzed processes is discussed and compared.