Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalNot applicablepeer-review

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Original languageEnglish
Pages (from-to)5560-5568
Journal / PublicationJournal of the American Chemical Society
Issue number16
Online published4 Apr 2018
Publication statusPublished - 25 Apr 2018
Externally publishedYes


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.