English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/155673
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:

Revisiting oxime-nitrone tautomerism. Evidence of nitrone tautomer participation in oxime nucleophilic addition reactions

AutorRoca-López, David ; Darù, Andrea; Tejero, Tomás ; Merino, Pedro
Fecha de publicación2016
EditorRoyal Society of Chemistry (Great Britain)
CitaciónRSC Advances 6(26): 22161-22173 (2016)
ResumenThe oxime-nitrone tautomerism has been revisited using high-level DFT calculations. The isomerization has been found to be more favorable through a bimolecular process involving two molecules of oxime, a finding that argues against the commonly accepted thermal 1,2-H-shift mechanism. The reaction of arylamidoximes with 1,2-diaza-1,3-dienes to yield the corresponding O-substituted oximes (stable intermediates for the synthesis of 1,2,4-oxadiazine derivatives) was also investigated as a rare case in which O-alkylation is observed in the reaction between oximes and electron-poor alkenes in the absence of a base. Under such conditions the reaction usually proceeds through the nucleophilic attack of the oxime nitrogen to yield the corresponding nitrone. The computational investigation revealed that in the case of arylamidoximes, the pathway involving the less stable but more reactive nitrone tautomer is the predominant mechanism, evidencing for the first time the involvement of a nitrone tautomer in nucleophilic additions of oximes. Validation of the model has been carried out by studying alternative ene-like processes; the dramatically different reactivity predicted for arylamidoximes and unsubstituted oxime are rationalized in terms of steric hindrance.
Versión del editorhttps://doi.org/10.1039/C6RA02638A
Identificadoresdoi: 10.1039/C6RA02638A
e-issn: 2046-2069
Aparece en las colecciones: (ISQCH) Artículos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
TautomerismEviden.pdf1,36 MBAdobe PDFVista previa
Mostrar el registro completo

Artículos relacionados:

NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.