A Designed Approach to Enantiodivergent Enamine Catalysis

Abstract The rational design and implementation of enantiodivergent enamine catalysis is reported. A simple secondary amine catalyst, 2‐methyl‐ l ‐proline, and its tetrabutylammonium salt function as an enantiodivergent catalyst pair delivering the enantiomers of α‐functionalized aldehyde products in excellent enantioselectivities. This novel concept of designed enantiodivergence is applied to the enantioselective α‐amination, aldol, and α‐aminoxylation/α‐hydroxyamination reactions of aldehydes.