A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with strained allenes

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dc.contributor.authorDomingo, L.R.
dc.contributor.authorRíos-Gutiérrez, M.
dc.contributor.authorPérez, P.
dc.date.accessioned2017-12-13T20:12:55Z
dc.date.available2017-12-13T20:12:55Z
dc.date.issued2017
dc.descriptionIndexación: Scopus.es_CL
dc.description.abstractThe [3 + 2] cycloaddition (32CA) reaction of C-phenyl-N-tert-butylnitrone with 1,2-cyclohexadiene (CHDE), a strained allene, has been studied within Molecular Electron Density Theory (MEDT) at the DFT B3LYP/6-311G(d,p) computational level. This non-polar 32CA reaction, which takes place through a non-concerted two-stage one-step mechanism, proceeds with a moderate Gibbs free activation energy of 22.7 kcal mol-1, and presents low stereo- and regioselectivities. The reaction begins by the creation of a pseudoradical center at the central carbon of the strained allene with a relatively low energy cost, which immediately promotes the formation the first C-C single bond. This scenario is completely different from that of the 32CA reaction involving the simplest allene. The strain present in CHDE changes its reactivity to that characteristic of radical species. Consequently, not distortion as previously proposed, but the radical reactivity type of the strained allene is responsible for the feasibility of this 32CA reaction.es_CL
dc.description.urihttp://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C7RA01916E#!divAbstract
dc.identifier.citationRSC Advances, 7(43) pp. 26879 - 26887es_CL
dc.identifier.issn2046-2069
dc.identifier.otherDOI: 10.1039/c7ra01916e
dc.identifier.urihttp://repositorio.unab.cl/xmlui/handle/ria/4888
dc.language.isoenes_CL
dc.publisherRoyal Society of Chemistryes_CL
dc.subjectActivation energyes_CL
dc.subjectCarbones_CL
dc.subjectComputation theoryes_CL
dc.subjectCycloadditiones_CL
dc.subjectElectron density measurementes_CL
dc.subjectHydrocarbonses_CL
dc.titleA molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with strained alleneses_CL
dc.typeArtículoes_CL
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