Computational Study of the Stability of Pyrrolidine-Derived Iminium Ions: Exchange Equilibria between Iminium Ions and Carbonyl Compounds

Primer Autor
Costa, Anna M.
Co-autores
Cascales, Victor
Castro-Alvarez, Alejandro
Vilarrasa, Jaume
Título
Computational Study of the Stability of Pyrrolidine-Derived Iminium Ions: Exchange Equilibria between Iminium Ions and Carbonyl Compounds
Editorial
AMER CHEMICAL SOC
Revista
ACS OMEGA
Lenguaje
en
Resumen
The tendency of carbonyl compounds to form Iminium ions by reaction with pyrrolidine or chiral pyrrolidine derivatives (in other words, the relative stability to hydrolysis of these iminium ions) has been computationally examined, mainly using the M06-2X/6-311+G(d,p) method. We have thus obtained the equilibrium positions for R-CH=O + CH2=CH-CH=N+R2* -> R-CH=N+R-2* + CH2=CH-CH=O reactions and for related exchanges. In these exchanges, there is a transfer of a secondary amine between two carbonyl compounds. Their relative energies may be used to predict which iminium species can be predominantly formed when two or more carbonyl groups are present in a reaction medium. In the catalytic Michael additions of nucleophiles to iminium ions arising from conjugated enals, dienals, and trienals, if the formation of the new Nu-C bond is favorable, the chances of amino-catalyzed reactions to efficiently proceed, with high conversions, depend on the calculated energy values for these exchange equilibria, where the iminium tetrafluoroborates of the adducts (final iminium intermediates) must be more prone to hydrolysis than the initial iminium tetrafluoroborates. The density functional theory (DFT) calculations indicate that the MacMillan catalysts and related oxazolidinones are especially suitable in this regard.
Tipo de Recurso
artículo original
doi
10.1021/acsomega.1c07020
Formato Recurso
PDF
Palabras Claves
AMINE
ORGANOCATALYSIS
MECHANISM
NITROMETHANE
CATALYSIS
ALDEHYDES
KETONES
SPIN
Ubicación del archivo
http://dx.doi.org/10.1021/acsomega.1c07020
Categoría OCDE
Química
Multidisciplinar
Materias
AMINA
ORGANOCATÁLISIS
MECANISMO
NITROMETANO
CATÁLISIS
ALDEHÍDOS
CETONAS
SPIN
Disciplinas de la OCDE
Química Orgánica
Físico-Química
Otras Especialidades de la Química
Título de la cita (Recomendado-único)
Computational Study of the Stability of Pyrrolidine-Derived Iminium Ions: Exchange Equilibria between Iminium Ions and Carbonyl Compounds
Página de inicio (Recomendado-único)
18247
Página final (Recomendado-único)
18258
Identificador del recurso (Mandatado-único)
artículo original
Versión del recurso (Recomendado-único)
version publicada
License
CC BY-NC-ND 4.0
Condición de la licencia (Recomendado-repetible)
CC BY-NC-ND 4.0
Derechos de acceso
acceso abierto
Access Rights
acceso abierto
Id de Web of Science
WOS:000818989300001
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