Mechanistic Understanding of Base-Catalyzed Aldimine/Ketoamine Condensations: An Old Story and A New Model

Aldimine/ketoamine condensations are basic reactions in chemical synthesis. Herein a density functional theory (DFT) study was performed to characterize the mechanism of the ketoamine condensation of acetophenone with tert-butanesulfinamide catalyzed by NaOH. The calculated results showed that the main N-tert-butanesulfinimines products own E configuration, which are due to both thermodynamic and kinetic effects. Meanwhile, the key roles of the substrate cage and the synergistic catalytic mode formed by metal cation and hydroxyl anion were pointed out, which imply the influence of noncovalent interactions on reaction activity. This theoretical study revealed the origin of E sulfinimines achieved in aldimine/ketoamine condensations catalyzed by base, which could provide new insights into the nature for the condensation reactions.

Automated summary

The study investigated the mechanism of ketoamine condensation catalyzed by NaOH using density functional theory (DFT), and found that the main products had E configuration. Additionally, the key roles of the substrate cage and the synergistic catalytic mode formed by metal cation and hydroxyl anion in influencing reaction activity were identified. This theoretical study provided new insights into the origin of E sulfinimines in aldImine/ketoamine condensations catalyzed by base.