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Authordc.contributor.authorGallardo Fuentes, Sebastián 
Authordc.contributor.authorContreras Ramos, Renato 
Admission datedc.date.accessioned2015-11-29T21:39:15Z
Available datedc.date.available2015-11-29T21:39:15Z
Publication datedc.date.issued2015
Cita de ítemdc.identifier.citationOrganic & Biomolecular Chemistry Volumen: 13 Número: 36 (2015)en_US
Identifierdc.identifier.otherDOI: 10.1039/c5ob01300c
Identifierdc.identifier.urihttps://repositorio.uchile.cl/handle/2250/135321
General notedc.descriptionArtículo de publicación ISIen_US
General notedc.descriptionSin acceso a texto completo
Abstractdc.description.abstractWe 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
Patrocinadordc.description.sponsorshipFondo de Innovacion para la Competitividad del Ministerio de Economia, Fomento y Turismo, Chile ICM: RC-130006- CILIS Conicyt 21120876en_US
Lenguagedc.language.isoenen_US
Publisherdc.publisherRoyal Soc Chemistryen_US
Keywordsdc.subjectFluorinated Heterocyclic-Compoundsen_US
Keywordsdc.subjectAromatic-Substitution Reactionsen_US
Keywordsdc.subjectDensity Functionalsen_US
Keywordsdc.subjectOrganic-Chemistryen_US
Keywordsdc.subjectHydrazineen_US
Keywordsdc.subject5-Perfluoroalkyl-1,2,4- Oxadiazolesen_US
Keywordsdc.subjectReactivitiesen_US
Keywordsdc.subjectNucleophileen_US
Keywordsdc.subjectIndazolesen_US
Keywordsdc.subjectKineticsen_US
Títulodc.titleMechanistic insights into the ANRORC-like rearrangement between methylhydrazine and 1,2,4-oxadiazole derivativesen_US
Document typedc.typeArtículo de revista


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