6533b831fe1ef96bd1298e02

RESEARCH PRODUCT

Density functional theory study of the mechanism of the proline-catalyzed intermolecular aldol reaction

Manuel ArnóLuis R. Domingo

subject

chemistry.chemical_classificationHajos–Parrish–Eder–Sauer–Wiechert reactionchemistry.chemical_compoundchemistryAldol reactionStereochemistryIntermolecular forceDensity functional theoryPhysical and Theoretical ChemistrySolvent effectsAldehydeIsobutyraldehydeEnamine

description

Transition structures associated with the C-C bond-formation step of the proline-catalyzed intermolecular aldol reaction between acetone and isobutyraldehyde have been studies using density functional theory methods at the B3LYP/6-31G** computational level. A continuum model has been selected to represent solvent effects. For this step, which is the stereocontrolling and rate-determining step, four reactive channels corresponding to the syn and anti arrangement of the active methylene of the enamine relative to the carboxylic acid group of l-proline and the re and si attack modes to both faces of the aldehyde carbonyl group have been analyzed. The B3LYP/6-31G** energies are in good agreement with experiment, allowing us to explain the origin of the catalysis and stereoselectivity for these proline-catalyzed aldol reactions.

https://doi.org/10.1007/s00214-002-0381-7