Author | dc.contributor.author | Gallardo Fuentes, Sebastián | |
Author | dc.contributor.author | Contreras Ramos, Renato | |
Admission date | dc.date.accessioned | 2015-11-29T21:39:15Z | |
Available date | dc.date.available | 2015-11-29T21:39:15Z | |
Publication date | dc.date.issued | 2015 | |
Cita de ítem | dc.identifier.citation | Organic & Biomolecular Chemistry Volumen: 13 Número: 36 (2015) | en_US |
Identifier | dc.identifier.other | DOI: 10.1039/c5ob01300c | |
Identifier | dc.identifier.uri | https://repositorio.uchile.cl/handle/2250/135321 | |
General note | dc.description | Artículo de publicación ISI | en_US |
General note | dc.description | Sin acceso a texto completo | |
Abstract | dc.description.abstract | We herein present the first in-depth theoretical study devoted to elucidate the mechanism of the
reaction between 1,2,4-oxadiazole derivatives and methylhydrazine. For this purpose, the
reaction between methylhydrazine and some polyfluoroaryl-1,2,4-oxadiazoles has been
employed as a model reaction. The analysis of the potential energy surface (PES) indicates that
the most favorable path involves an initial amine attack at the C(2') site of the aryl moiety to
yield an aryl-hydrazine intermediate whose thermodynamic stability appears as the main
determinant of the favored reaction path. Next, the cyclization step leading to a spiro
intermediate through a favored 5-exo-trig process appears as the rate determining step.
Additionally, this study highlights the relevance of the torsional strain effects on the favored
ANRORC pathway. Finally, both the origins of the substituent effects on the regioselectivity
patterns as well as the need of using a large excess of nucleophile to afford the favored
ANRORC pathway are discussed. | en_US |
Patrocinador | dc.description.sponsorship | Fondo de Innovacion para la Competitividad del Ministerio de
Economia, Fomento y Turismo, Chile
ICM: RC-130006-
CILIS
Conicyt 21120876 | en_US |
Lenguage | dc.language.iso | en | en_US |
Publisher | dc.publisher | Royal Soc Chemistry | en_US |
Keywords | dc.subject | Fluorinated Heterocyclic-Compounds | en_US |
Keywords | dc.subject | Aromatic-Substitution Reactions | en_US |
Keywords | dc.subject | Density Functionals | en_US |
Keywords | dc.subject | Organic-Chemistry | en_US |
Keywords | dc.subject | Hydrazine | en_US |
Keywords | dc.subject | 5-Perfluoroalkyl-1,2,4- Oxadiazoles | en_US |
Keywords | dc.subject | Reactivities | en_US |
Keywords | dc.subject | Nucleophile | en_US |
Keywords | dc.subject | Indazoles | en_US |
Keywords | dc.subject | Kinetics | en_US |
Título | dc.title | Mechanistic insights into the ANRORC-like rearrangement between methylhydrazine and 1,2,4-oxadiazole derivatives | en_US |
Document type | dc.type | Artículo de revista | |