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dc.contributor.authorNúñez-Villanueva, D.-
dc.contributor.authorBonache de Marcos, María Ángeles-
dc.contributor.authorLozano, L.-
dc.contributor.authorInfantes, L.-
dc.contributor.authorElguero, José-
dc.contributor.authorAlkorta, Ibon-
dc.contributor.authorGarcía-López, M. Teresa-
dc.contributor.authorGonzález-Muñiz, Rosario-
dc.contributor.authorMartín-Martínez, Mercedes-
dc.identifierdoi: 10.1002/chem.201405640-
dc.identifierissn: 0947-6539-
dc.identifiere-issn: 1521-3765-
dc.identifier.citationChemistry - A European Journal 21: 2489-2500 (2015)-
dc.description.abstractEnantiopure β-amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4-carboxy-2-oxoazepane α,α-amino acids to lead to 2′-oxopiperidine-containing β2,3,3- amino acids, upon basic or acid hydrolysis of the 2-oxoazepane α,α-amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six-membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4-carboxylic acid substituted 2-oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2-oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.-
dc.publisherJohn Wiley & Sons-
dc.subjectamino acids-
dc.subjectdensity functional calculations-
dc.subjectintramolecular catalysis-
dc.titleExperimental and theoretical studies on the rearrangement of 2-oxoazepane α,α-amino acids into 2′-oxopiperidine β2,3,3-amino acids: An example of intramolecular catalysis-
dc.description.versionPeer Reviewed-
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