Dynamic Covalent Metathesis in the C=C/C=N exchange between Knoevenagel Compounds and Imines,Journal of the American Chemical Society

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Dynamic Covalent Metathesis in the C=C/C=N exchange between Knoevenagel Compounds and Imines
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-04-04 , DOI: 10.1021/jacs.8b01849
Ruirui Gu _{1,

2} , Karolina Flidrova ₁ , Jean-Marie Lehn ₁

Affiliation

Fast and reversible dynamic covalent C═C/C═N exchange takes place without catalyst in nonpolar solvents between barbiturate-derived Knoevenagel (Kn) compounds and imines. A detailed study of the reaction indicates that it proceeds by an associative organo-metathesis mechanism involving the formation of a four-membered ring azetidine intermediate by addition of the imine C═N group to the C═C bond of the Kn compound. This intermediate could be generated cleanly and stabilized at low temperature by condensation of the o,p-dinitrophenyl Kn derivative with the cyclic imine 1-azacyclohexene. It was characterized by extensive NMR and mass spectrometric studies. The process described represents a genuine dynamic covalent organo-metathesis through a four-membered ring adduct as intermediate. It paves the way for the exploration of a wide set of dynamic systems involving (strongly) polarized C═C bonds and various imines, extending also into covalent dynamic polymers and polymolecular assemblies.

中文翻译：

Knoevenagel 化合物和亚胺之间 C=C/C=N 交换中的动态共价复分解

在巴比妥酸盐衍生的 Knoevenagel (Kn) 化合物和亚胺之间的非极性溶剂中，无需催化剂即可发生快速且可逆的动态共价 C=C/C=N 交换。对该反应的详细研究表明，它通过缔合有机复分解机制进行，包括通过将亚胺 C=N 基团添加到 Kn 化合物的 C=C 键形成四元环氮杂环丁烷中间体。该中间体可以通过邻，对二硝基苯基 Kn 衍生物与环状亚胺 1-氮杂环己烯的缩合而在低温下干净地生成并稳定。它的特点是广泛的核磁共振和质谱研究。所描述的过程代表了通过四元环加合物作为中间体的真正动态共价有机复分解。

更新日期：2018-04-04

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