Catalysis by Bidentate Iodine(III)-Based Halogen Donors: Surpassing the Activity of Strong Lewis Acids.

ABSTRACT: The poorly understood mode of activation and catalysis of bidentate iodine(III)-based halogen donors have been quantitatively explored in detail by means of state-of-the-art computational methods. To this end, the uncatalyzed Diels-Alder cycloaddition reaction between cyclohexadiene and methyl vinyl ketone is compared to the analogous process mediated by a bidentate iodine(III)-organocatalyst and by related, highly active iodine(I) species. It is found that the bidentate iodine(III)-catalyst accelerates the cycloaddition by lowering the reaction barrier up to 10 kcal mol^-1 compared to the parent uncatalyzed reaction. Our quantitative analyses reveal that the origin of the catalysis is found in a significant reduction of the steric (Pauli) repulsion between the diene and dienophi

SUBMITTER: Portela S 

PROVIDER: S-EPMC9132362 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature