6533b831fe1ef96bd1298e02
RESEARCH PRODUCT
Density functional theory study of the mechanism of the proline-catalyzed intermolecular aldol reaction
Manuel ArnóLuis R. Domingosubject
chemistry.chemical_classificationHajos–Parrish–Eder–Sauer–Wiechert reactionchemistry.chemical_compoundchemistryAldol reactionStereochemistryIntermolecular forceDensity functional theoryPhysical and Theoretical ChemistrySolvent effectsAldehydeIsobutyraldehydeEnaminedescription
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.
year | journal | country | edition | language |
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2002-10-01 | Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta) |