Imidazolidinone intermediates in prolinamide-catalyzed aldol reactions.
The reaction between acetone and 4-nitrobenzaldehyde catalyzed by aniline prolinamide 1 was studied in depth. Working in different solvents with equimolar amounts of reagents and monitoring the reaction by 1H NMR, we detected and identified several imidazolidinones, such as those of the acetone 4, the aldol products 5a and 5b, and aldehydes 10a and 10b. According to our results, these compounds could influence the reaction rate and diminish product enantioselectivity. Furthermore, acetone imidazolidinone 4 was seen to react with 4-nitrobenzaldehyde to furnish the aldol product 3. This reaction can be catalyzed by different nucleophiles and acids. In fact, strong acids such as camphorsulfonic or trifluoroacetic acid, convert imidazolidinones into iminium salts and afford more enantioselective aldol reactions when different aromatic prolinamides are used. Enantiomeric excesses of ca. 82% are reached.
Fuentes de Arriba
Angel L
AL
Departamento de Química Orgánica, Universidad de Salamanca, Plaza de los Caídos 1-5, E-37008, Salamanca, Spain.
Simón
Luis
L
Raposo
César
C
Alcázar
Victoria
V
Sanz
Francisca
F
Muñiz
Francisco M
FM
Morán
Joaquín R
JR