Epoxidation of unfunctionalized olefins by Mn(salen) catalyst using organic peracids as oxygen source: a theoretical study.

The mechanism and origin of asymmetric induction in the Mn(III)(salen)-catalyzed epoxidation by peracetic acid have been elucidated by the density functional [Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional (B3LYP)] method in two different regimes: with and without an axial ligand. The acylperoxo complexes of Mn(II,III,IV) in cisON cisNO and trans geometrical configurations cannot compete with the catalyst-free Prilezhaev epoxidation. Instead, oxo species perform epoxidation following the O-O bond cleavage in the acylperoxo complexes. The epoxidation may proceed in a concerted and/or radical-mediated stepwise manner. The actual mechanism of the epoxidation depends on the electronic and oxidation state of the oxo species and the nature of the axial ligand. The olefin can approach the reactive MnO fragment of both cis and trans-l-isomers of the plain oxo species along multiple distinct directions: native approaches. The native approaches are used to rationalize the inversion of the absolute configuration of the product epoxide due to the axial ligand.