Versatile One-Pot Synthesis of Polysubstituted Cyclopent-2-enimines from α,β-Unsaturated Amides: Imino-Nazarov Reaction
Versatile One-Pot Synthesis of Polysubstituted Cyclopent-2-enimines from α,β-Unsaturated Amides: Imino-Nazarov Reaction
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从 α,β-不饱和酰胺一锅法合成多取代环戊-2-烯胺：亚氨基-纳扎罗夫反应
DOI：
10.1002/anie.201805641
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发表时间：
2018-08-06
影响因子：
16.6
通讯作者：
Huang, Pei-Qiang
中科院分区：
文献类型：
--
作者：
Fan, Ting;Wang, Ao;Huang, Pei-Qiang
实现了多取代戊烷-1，4-二烯-3-亚胺的亚氨基-纳扎罗夫环化反应。为此，系统地研究了α，β-不饱和仲酰胺与有机三氟硼酸钾还原的烯亚胺化反应，以及多取代戊烷-1，4-二烯-3-亚胺中间体的酸催化亚氨基-纳扎罗夫环化反应。这种温和、操作简单、灵活和高产率的方案有效地提供了多取代的戊烷-1，4-二烯-3-亚胺、环戊烯亚胺和α-氨基环戊酮，它们是有机合成中有用的支架。用密度泛函理论方法研究了多取代戊烷-1，4-二烯-3-亚胺在C2位的取代基效应。结果表明，供电子基团促进了亚氨基-纳扎罗夫环化反应。
The imino-Nazarov cyclization of the polysubstituted pentan-1,4-diene-3-imines was realized. To this aim, a one-pot procedure involving reductive alkenyliminylation of alpha,beta-unsaturated secondary amides with potassium organotrifluoroborates, followed by acid-catalyzed imino-Nazarov cyclization of the polysubstituted pentan-1,4-diene-3-imine intermediates, was studied systematically. This mild, operationally simple, flexible, and high-yielding protocol efficiently affords polysubstituted pentan-1,4-diene-3-imines, cyclopentenimines, and alpha-amino cyclopentenones, which are useful scaffolds in organic synthesis. The substituent effect at the C2 position of the polysubstituted pentan-1,4-diene-3-imines was studied by means of density-functional theory calculations. Results suggested that the electron-donating group facilitates the imino-Nazarov cyclization process.