Deciphering the Curly Arrow Representation and Electron Flow for the 1,3-Dipolar Rearrangement between Acetonitrile Oxide and (1S,2R,4S)-2-Cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl Acetate Derivatives
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Otros documentos de la autoría: ADJIEUFACK , Abel Idrice; Nana, Cyrille Nouhou; Ketcha-Mbadcam, Joseph; MBOUOMBOUO NDASSA, Ibrahim; Andres, Juan; Oliva, Mónica; Safont Villarreal, Vicent Sixte
Metadatos
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INVESTIGACIONMetadatos
Título
Deciphering the Curly Arrow Representation and Electron Flow for the 1,3-Dipolar Rearrangement between Acetonitrile Oxide and (1S,2R,4S)-2-Cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl Acetate DerivativesAutoría
Fecha de publicación
2020-09-08Editor
American Chemical SocietyISSN
2470-1343Cita bibliográfica
Adjieufack, A. I., Nana, C. N., Ketcha-Mbadcam, J., Mbouombouo Ndassa, I., Andrés, J., Oliva, M.; Safont, V. S. Deciphering the Curly Arrow Representation and Electron Flow for the 1,3-Dipolar Rearrangement between Acetonitrile Oxide and (1S,2R,4S)-2-Cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl Acetate Derivatives. ACS Omega 2020, 5, 35, 22215–22225, DOI: 10.1021/acsomega.0c02371Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://pubs.acs.org/doi/10.1021/acsomega.0c02371Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
This study is focused on describing the molecular mechanism beyond the molecular picture provided by the evolution of molecular orbitals, valence bond structures along the reaction progress, or conceptual density ... [+]
This study is focused on describing the molecular mechanism beyond the molecular picture provided by the evolution of molecular orbitals, valence bond structures along the reaction progress, or conceptual density functional theory. Using bonding evolution theory (BET) analysis, we have deciphered the mechanism of the 1,3-dipolar rearrangement between acetonitrile oxide and (1S,2R,4S)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl acetate derivatives. The BET study revealed that the formation of the C–C bond takes place via a usual sharing model before the O–C one that is also formed in the halogenated species through a not very usual sharing model. The mechanism includes depopulation of the electron density at the N–C triple bond and creation of the V(N) and V(C) monosynaptic basins, depopulation of the former C–C double bond with the creation of V(C,C) basins, and final formation of the V(O,C) basin associated with the O–C bond. The topological changes along the reaction pathway take place in a highly synchronous way. BET provides a convenient quantitative method for deriving curly arrows and electron flow representation to unravel molecular mechanisms. [-]
Publicado en
ACS Omega, 2020, vol. 5, no 35Proyecto de investigación
Fonds de la Recherche Scientifique - FNRS; Walloon Region; University of Namur: 2.5020.11, GEQ U.G006.15, 1610468, RW/GEQ2016; Universitat Jaume I: UJI-B2019-30; Ministerio de Ciencia, Innovacio'n y Universidades (Spain): PGC2018-094417-B-I00Derechos de acceso
This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Copyright © American Chemical Society
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