Specific nucleophile–electrophile interactions in nucleophilic aromatic substitutions

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dc.contributor.authorOrmazábal-Toledo, Rodrigo
dc.contributor.authorContreras, Renato
dc.contributor.authorTapia, Ricardo
dc.contributor.authorCampodónico, Paola
dc.date.accessioned2017-04-10T13:19:34Z
dc.date.available2017-04-10T13:19:34Z
dc.date.issued2013
dc.descriptionCentro de Química Médica
dc.description.abstractWe herein report results obtained from an integrated experimental and theoretical study on aromatic nucleophilic substitution (S(N)Ar) reactions of a series of amines towards 1-fluoro-2,4-dinitrobenzene in water. Specific nucleophile-electrophile interactions in the title reactions have been kinetically evaluated. The whole series undergoes S(N)Ar reactions where the formation of the Meisenheimer complex is rate determining. Theoretical studies concerning specific interactions are discussed in detail. It is found that H-bonding effects along the intrinsic reaction coordinate profile promote the activation of both the electrophile and the nucleophile. Using these results, it is possible to establish a hierarchy of reactivity that is in agreement with the experimental data. Second order energy perturbation energy analysis highlights the strong interaction between the ortho-nitro group and the acidic hydrogen atom of the amine. The present study strongly suggests that any theoretical analysis must be performed at the activated transition state structure, because the static model developed around the reactant states hides most of the relevant specific interactions that characterize the aromatic substitution process.
dc.format.extent8
dc.identifier.citationOrganic & Biomolecular Chemistry, 2013, 14;11(14):2302-2309
dc.identifier.urihttp://hdl.handle.net/11447/1120
dc.identifier.urihttp://dx.doi.org/10.1039/c3ob27450k
dc.language.isoen_US
dc.publisherRoyal Society of Chemistry
dc.subjectAmines/chemistry
dc.subjectDinitrofluorobenzene/chemistry
dc.subjectModels, Molecular
dc.subjectWater/chemistry
dc.titleSpecific nucleophile–electrophile interactions in nucleophilic aromatic substitutions
dc.typeArtículo

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