Repositorio UFRO · Omeka S

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
Versión del recurso (Recomendado-único)	version publicada
Tipo de ruta	dorada verde
Access Rights	acceso abierto
Derechos de acceso	acceso abierto
Id de Web of Science	WOS:000818989300001
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
License	CC BY-NC-ND 4.0
Condición de la licencia (Recomendado-repetible)	CC BY-NC-ND 4.0