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Evidence for an enolate mechanism in the asymmetric Michael reaction of α,β-unsaturated aldehydes and ketones via a hybrid system of two secondary amine catalysts

The key nucleophile was found to be neither an enamine nor an enol, but an enolate in the direct Michael reaction of α,β-unsaturated aldehydes and non-activated ketones catalyzed by two amine catalysts namely diphenylprolinol silyl ether and pyrrolidine. This is a rare example of an enolate from a k...

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Detalles Bibliográficos
Autores principales: Umekubo, Nariyoshi, Terunuma, Takahiro, Kwon, Eunsang, Hayashi, Yujiro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8162273/
https://www.ncbi.nlm.nih.gov/pubmed/34094371
http://dx.doi.org/10.1039/d0sc03359f
Descripción
Sumario:The key nucleophile was found to be neither an enamine nor an enol, but an enolate in the direct Michael reaction of α,β-unsaturated aldehydes and non-activated ketones catalyzed by two amine catalysts namely diphenylprolinol silyl ether and pyrrolidine. This is a rare example of an enolate from a ketone serving as a key intermediate in the asymmetric organocatalytic reaction involving secondary amine catalysts because the ketone enolates are generally generated using a strong base, and the enamine is a common nucleophile in this type of reaction.