Computational and Experimental Studies on the α-Functionalization of Ketones Using Domino Reactions: A Strategy to Increase Chemoselectivity at the α-Carbon of Ketones.

ABSTRACT: A facile strategy to increase the chemoselectivity of domino reactions was proposed and successfully applied in the α-functionalization of ketones. The strategy involved widening the activation energy of the main reaction and side reaction through intermolecular interactions, thereby increasing the chemoselectivity of the domino reaction. In the proposed α-functionalization reaction, TMSCF₃ acted as an excellent reagent which increased the nucleophilicity of DMF through the Van der Waals force and reduced the nucleophilicity of H₂O through a hydrogen bond. We found that TMSCF₃ can increase the activation energy difference between the main reaction and side reaction using DFT calculations, which greatly increased chemoselectivity and avoided the formation of

SUBMITTER: Sun H 

PROVIDER: S-EPMC11901711 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature