Origin of the enantioselectivity in organocatalytic Michael additions of ß-ketoamides to α,ß-unsaturated carbonyls: a combined experimental, spectroscopic and theoretical study.
Chemistry
; 21(2): 778-90, 2015 Jan 07.
Article
em En
| MEDLINE
| ID: mdl-25382666
ABSTRACT
The organocatalytic enantioselective conjugate addition of secondary ß-ketoamides to α,ß-unsaturated carbonyl compounds is reported. Use of bifunctional Takemoto's thiourea catalyst allows enantiocontrol of the reaction leading either to simple Michael adducts or spirocyclic aminals in up to 99 %â
ee. The origin of the enantioselectivity has been rationalised based on combined DFT calculations and kinetic analysis. This study provides a deeper understanding of the reaction mechanism, which involves a predominant role of the secondary amide proton, and clarifies the complex interactions occurring between substrates and the catalyst.
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Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Amidas
/
Nitrilas
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2015
Tipo de documento:
Article