The Outcome of the Oxidations of Unusual Enediamide Motifs Is Governed by the Stabilities of the Intermediate Iminium Ions

We compare the results from the oxidation of two unusual “enediamide” motifs (3,4-dihydropyrazin-2(1H)-ones), where a double bond is flanked by two amides. In one case the oxidation led to a ring-opened product arising from the cleavage of the double bond, and in the other a rare cis-dioxygenated co...

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Detalles Bibliográficos
Autores principales: Ahamed, Muneer, Chan, Bun, Jensen, Paul, Todd, Matthew H.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Public Library of Science 2012
Materias:
Research Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3477162/
https://www.ncbi.nlm.nih.gov/pubmed/23094038
http://dx.doi.org/10.1371/journal.pone.0047224
Descripción
Sumario:We compare the results from the oxidation of two unusual “enediamide” motifs (3,4-dihydropyrazin-2(1H)-ones), where a double bond is flanked by two amides. In one case the oxidation led to a ring-opened product arising from the cleavage of the double bond, and in the other a rare cis-dioxygenated compound was obtained. Both products have been characterized by X-ray crystallography. The outcomes of the key reactions are rationalized based on calculated free energies of intermediates.

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