Collect. Czech. Chem. Commun. 2007, 72, 715-727

The Mechanism of the Permanganate-Promoted Oxidative Cyclization of 1,5-Dienes - a DFT Study

Alexander Poethig and Thomas Strassner*

Professur für Physikalische Organische Chemie, Technische Universität Dresden, 01062 Dresden, Germany


The mechanism of the permanganate oxidation of 1,5-dienes was investigated by density functional theory calculations (B3LYP/6-311+G*). The experimentally observed (unexpected) products, 2,5-bis(hydroxymethyl) tetrahydrofurans, are formed in a concerted reaction, which explains the observed stereoselectivity of the reaction. Water plays an important role in the reaction mechanism by significantly lowering the activation energies.

Keywords: Permanganate; DFT calculations; Oxidations; Alkenes; Dienes; Stereoselectivity; Tetrahydrofurans; Reaction mechanism; Oxidative cyclizations.

References: 73 live references.