Establishing the (3 + 2) Mechanism for the Permanganate Oxidation of Alkenes by Theory and Kinetic Isotope Effects

K. N. Houk; Thomas Strassner

doi:10.1021/jo981548f

Establishing the (3 + 2) Mechanism for the Permanganate Oxidation of Alkenes by Theory and Kinetic Isotope Effects

J Org Chem. 1999 Feb 5;64(3):800-802. doi: 10.1021/jo981548f.

Authors

K. N. Houk¹, Thomas Strassner

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, and Department of Inorganic Chemistry, Technical University Munich, Lichtenbergstrasse 4, D-85747 Garching, Germany.

PMID: 11674149
DOI: 10.1021/jo981548f

Abstract

Permanganate hydroxylation follows the (3 + 2) cycloaddition mechanism established earlier for osmium tetroxide. Density functional theory (Becke3LYP/6-31G) predicts that the concerted (3 + 2) pathway is favored by about 40 kcal/mol relative to a stepwise process involving a (2 + 2) cycloaddition. The activation energy for the (3 + 2) transition state is calculated to be only 9.2 kcal/mol. The energetics are remarkably similar to the results for osmylation, where the activation energies are calculated to be 3.2 kcal/mol for the (3 + 2) and 44.1 kcal/mol for the (2 + 2) transition state. Calculated kinetic isotope effects for a substituted case are in good agreement with experiment.