Old tricks, new dogs: organocatalytic dienamine activation of α,β-unsaturated aldehydes.
Old tricks, new dogs: organocatalytic dienamine activation of α,β-unsaturated aldehydes.
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DOI：
10.1039/c6cs00438e
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发表时间：
2016-12-21
影响因子：
46.2
通讯作者：
Alemán J
中科院分区：
文献类型：
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作者：
Marcos V;Alemán J
在这里，我们概述和讨论的国家的最先进的有机催化二烯胺活化烯醛，分类的例子，根据不同的反应活化途径。手性仲胺是一些最常用的催化剂种类。它们已成为羰基化合物通过HOMO、SOMO或LUMO活化途径进行α-和β-活化的可靠工具。最近，化学家们已经将注意力转向开发用于远程官能化的新型有机催化策略，通过二烯胺、三烯胺和乙烯基亚胺离子途径（分别为γ-、ε-和δ-位置）靶向甚至更远离催化剂活化位点的立体中心。在这里，我们概述并讨论了二烯胺活化的最新技术，根据形成的二烯胺中间体（1，3-，1，5-，2，5-和4，5-官能化）和反应类型的不同反应活化途径对实例进行分类，这些反应类型由亲电体和亲核体的结构和性质决定。
Here we outline and discuss the state-of-the-art in organocatalytic dienamine activation of enals, classifying examples according to different reactive activation pathways. Chiral secondary amines are some of the most commonly used kinds of catalysts. They have become a reliable tool for the α- and β-activation of carbonyl compounds, via HOMO, SOMO or LUMO activation pathways. Recently, chemists have turned their attention to the development of novel organocatalytic strategies for remote functionalisation, targeting stereocentres even more distant from the catalyst-activation site, through dienamine, trienamine, and vinylogous iminium ion pathways (γ-, ε- and δ-positions, respectively). Here we outline and discuss the state-of-the-art in dienamine activation, classifying examples according to the different reactive activation pathways followed by the formed dienamine intermediate (1,3-, 1,5-, 2,5- and 4,5-functionalisation) and the reaction type developed, as determined by the structure and the nature of electrophiles and nucleophiles.