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Título: | Mechanism switch in Mannich-type reactions. ELF and NCI topological analyses of the reaction between nitrones and lithium enolates |
Autor: | Roca-López, David CSIC ORCID; Polo, Víctor CSIC ORCID; Tejero, Tomás CSIC ORCID; Merino, Pedro CSIC ORCID | Palabras clave: | Nitrones Mannich reaction Enolates Reaction mechanisms |
Fecha de publicación: | 2015 | Editor: | Wiley-VCH | Citación: | European Journal of Organic Chemistry 19: 4143-4152 (2015) | Resumen: | The mechanism of the addition of lithium enolates derived from esters, ketones and aldehydes to nitrones (Mannich-type reaction) has been studied using DFT methods. While the reactions with α-methoxy and α-methyl enolates takes place through a stepwise mechanism, consisting of an initial nucleophilic attack of the enolate to the nitrone carbon followed by a second nucleophilic attack of the nitrone oxygen to the formed carbonyl group, the reaction with α-unsusbtituted enolates takes place through a one-step mechanism. The IRC analysis shows the presence of a hidden intermediate in agreement with one kinetic step two stages process. The topological analysis of the electronic localization function (ELF) confirms that only when the first C-C bond is formed, does the C-O bond formation begin. The NCI analyses, are also in agreement with the formation of intermediates for α-methoxy and α-methyl enolates and a highly asynchronous one-step process in the case of α-unsusbtituted enolates. | Versión del editor: | http://dx.doi.org/10.1002/ejoc.201500447 | URI: | http://hdl.handle.net/10261/122612 | DOI: | 10.1002/ejoc.201500447 | ISSN: | 1434-193X | E-ISSN: | 1099-0690 |
Aparece en las colecciones: | (ISQCH) Artículos |
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Mechanism Switch in Mannich.pdf | 1,3 MB | Adobe PDF | Visualizar/Abrir |
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