How Lewis Acids Catalyze Ring-Openings of Cyclohexene Oxide.

ABSTRACT: We have quantum chemically studied the Lewis acid-catalyzed epoxide ring-opening reaction of cyclohexene epoxide by MeZH (Z = O, S, and NH) using relativistic dispersion-corrected density functional theory. We found that the reaction barrier of the Lewis acid-catalyzed epoxide ring-opening reactions decreases upon ascending in group 1 along the series Cs⁺ > Rb⁺ > K⁺ > Na⁺ > Li⁺ > H⁺. Our activation strain and Kohn-Sham molecular orbital analyses reveal that the enhanced reactivity of the Lewis acid-catalyzed ring-opening reaction is caused by the reduced steric (Pauli) repulsion between the filled orbitals of the epoxide and the nucleophile, as the Lewis acid polarizes the filled orbitals of the epoxide more efficiently away

SUBMITTER: Hansen T 

PROVIDER: S-EPMC7901664 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature