Mechanism of the permanganate-promoted oxidative cyclization of 1,5-dienes: A DFT study

ORGN 539

Thomas Strassner, thomas.strassner@chemie.tu-dresden.de and Alexander Poethig. Physical Organic Chemistry, TU Dresden, Mommsenstrasse 13, Dresden, 01062, 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) substituted 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.