Theory of asymmetric organocatalysis of aldol and related reactions: Rationalizations and predictions

Computational studies have led to models to understand some classic and contemporary asymmetric reactions involving organo-catalysts. The Hajos-Parrish-Eder-Sauer-Wiechert reaction and intermolecular aldol reactions as well as Mannich reactions and oxyaminations catalyzed by proline and other amino acids, and Diels-Alder reactions catalyzed by MacMillan's chiral amine organocatalysts have been studied with density functional theory. Quantitative predictions for several new catalysts and reactions are provided.