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dc.contributor.authorMartí-Centelles, Vicente
dc.contributor.authorBurguete, M. Isabel
dc.contributor.authorCativiela, Carlos
dc.contributor.authorLuis, Santiago V.
dc.date.accessioned2015-07-16T10:22:04Z
dc.date.available2015-07-16T10:22:04Z
dc.date.issued2013-12
dc.identifier.citationMARTÍ-CENTELLES, Vicente, et al. The Role of the Amino Acid-Derived Side Chain in the Preorganization of C 2-Symmetric Pseudopeptides: Effect on SN2 Macrocyclization Reactions. The Journal of organic chemistry, 2013, 79.2: 559-570.ca_CA
dc.identifier.urihttp://hdl.handle.net/10234/127825
dc.description.abstractA family of pseudopeptidic macrocycles containing non-natural amino acids have been synthesized. The macrocyclization reaction has been studied experimentally and computationally, demonstrating the key role of both the amino acid side chain and the catalytic bromide anion. The bromide anion acts as an external template assisting the folding of the open-chain precursor in a proper conformation. Computations revealed that in the presence of the anion, the effect of the side chain on the energy barrier for the macrocyclization is very small. However, the effect on the conformational equilibria of the open-chain precursors is very important. Overall, the stabilization of those conformation(s) in which the two reactive ends of the open-chain intermediate are located at short distances from each other with the correct orientation is the critical parameter defining the success of the macrocyclization. The best yield was found for the compound containing cyclohexylalanine, for which the computationally-predicted most stable conformer in the presence of Br– has a proper preorganization for cyclization. The remarkable agreement obtained between experiments and theory reveals that the computational approach here considered can be of great utility for the prediction of the behavior of other related systems and for the design of appropriate synthetic routes to new macrocyclic compounds.ca_CA
dc.format.extent11 p.ca_CA
dc.format.mimetypeapplication/pdfca_CA
dc.language.isoengca_CA
dc.publisherAmerican Chemical Societyca_CA
dc.relation.isPartOfJ. Org. Chem., 2014, 79 (2)ca_CA
dc.rightsCopyright © 2013 American Chemical Societyca_CA
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/*
dc.subjectAmino acidsca_CA
dc.subjectMacrocyclization reactionsca_CA
dc.subjectMacrocyclic Compoundsca_CA
dc.subjectCyclizationca_CA
dc.subjectIonsca_CA
dc.subjectmolca_CA
dc.titleThe Role of the Amino Acid Derived Side Chain in the Preorganization of C2 Symmetric Pseudopeptides: Effect on SN2 Macrocyclization Reactionsca_CA
dc.typeinfo:eu-repo/semantics/articleca_CA
dc.identifier.doihttp://dx.doi.org/10.1021/jo4022309
dc.rights.accessRightsinfo:eu-repo/semantics/restrictedAccessca_CA
dc.relation.publisherVersionhttp://pubs.acs.org/doi/abs/10.1021/jo4022309ca_CA


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