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dc.contributor.author
Vallejos, Margarita
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dc.contributor.author
Pellegrinet, Silvina Carla
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dc.date.available
2016-06-06T21:09:57Z
dc.date.issued
2015-05
dc.identifier.citation
Vallejos, Margarita; Pellegrinet, Silvina Carla; Competing mechanisms for the reaction of dichloropropynylborane with 2-tert-butylbutadiene. Diels-Alder reaction versus alkynylboration; Royal Society of Chemistry; RSC Advances; 5; 86; 5-2015; 70147-70155
dc.identifier.issn
2046-2069
dc.identifier.uri
http://hdl.handle.net/11336/6064
dc.description.abstract
Density functional theory and the quantum theory of atoms in molecules approach were used to study two competing process: the Diels-Alder reaction (DA) and the 1,4-alkynylboration (AB) between dichloropropynylborane (1) and 2-tertbutylbutadiene (2) in dichloromethane. We analyzed several reaction pathways related with such reactions for both orientations (meta and para). The stepwise mechanisms for the two competitive reactions share the first step that leads toan intermediate zwitterionic structure. The second step is more favorable for the reaction occurring via TSC-m that leads to the meta enyne product 5, which is the kinetic product. The formation of the meta DA product cannot be explainedthrough a direct cycloaddition, due to the higher activation free energy of the associated transition structure (TSB-m). An alternative transition structure with [4 + 3] character (TSD-m) that connects the meta enyne 5 with the meta cycloadduct 3 was found. We propose that at longer reaction times, 5 rearranges to the thermodynamic product 3 via TSD-m passing by a six-membered ring structure and a seven-membered ring structure. The topological analysis of the charge density along the selected reaction coordinates provided some understanding on the intriguing competitive reactions.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.subject
Diels-Alder Reaction
dc.subject
Alkynylboration
dc.subject.classification
Química Orgánica
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Competing mechanisms for the reaction of dichloropropynylborane with 2-tert-butylbutadiene. Diels-Alder reaction versus alkynylboration
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-06-01T13:48:42Z
dc.journal.volume
5
dc.journal.number
86
dc.journal.pagination
70147-70155
dc.journal.pais
Reino Unido
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dc.journal.ciudad
Cambridge
dc.description.fil
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura; Argentina
dc.description.fil
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
dc.journal.title
RSC Advances
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/ra/2015/c5ra12903f
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/C5RA12903F
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