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Experimental 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

AuthorsNúñez-Villanueva, D. ; Bonache de Marcos, María Ángeles ; Lozano, L.; Infantes, L. ; Elguero, José ; Alkorta, Ibon ; García-López, M. Teresa ; González-Muñiz, Rosario ; Martín-Martínez, Mercedes
amino acids
density functional calculations
intramolecular catalysis
Issue Date2015
PublisherJohn Wiley & Sons
CitationChemistry - A European Journal 21: 2489-2500 (2015)
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.
Identifiersdoi: 10.1002/chem.201405640
issn: 0947-6539
e-issn: 1521-3765
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(IQM) Artículos
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