The Role of the Amino Acid Derived Side Chain in the Preorganization of C2 Symmetric Pseudopeptides: Effect on SN2 Macrocyclization Reactions
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Otros documentos de la autoría: Martí-Centelles, Vicente; Burguete, M. Isabel; Cativiela, Carlos; Luis, Santiago V.
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http://dx.doi.org/10.1021/jo4022309 |
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Título
The Role of the Amino Acid Derived Side Chain in the Preorganization of C2 Symmetric Pseudopeptides: Effect on SN2 Macrocyclization ReactionsFecha de publicación
2013-12Editor
American Chemical SocietyCita bibliográfica
MARTÍ-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.Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.acs.org/doi/abs/10.1021/jo4022309Palabras clave / Materias
Resumen
A 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 ... [+]
A 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. [-]
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J. Org. Chem., 2014, 79 (2)Derechos de acceso
Copyright © 2013 American Chemical Society
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