The catalytic properties of a series of chiral nonheme aminopyridinylmanganese(II) complexes [LMnII(OTf)(2)] were investigated. The above complexes were found to efficiently catalyze enantioselective olefin oxidation to the corresponding epoxides with different oxidants (peroxycarboxylic acids, alkyl hydroperoxides, iodosylarenes, etc.) with high conversions and selectivities (up to 100%) and enantiomeric excesses (up to 79%). The effect of the ligand structure on the catalytic performance was probed. Epoxidation enantioselectivities were found to be strongly dependent on the structure of the oxidants (performic, peracetic, and m-chloroperbenzoic acids; tert-butyl and cumyl hydroperoxides; iodosylbenzene and iodosylmesitylene), thus bearing evidence that the terminal oxidant molecule is incorporated in the structure of the oxygen-transferring intermediates. High-valence electron-paramagnetic-resonance-active manganese complexes [LMnIV=O](2+) and [LMnIV(mu-O)(2)(MnL)-L-III](3+) were detected upon interaction of the starting catalyst with the oxidants. The high-valence complexes did not epoxidize styrene and could themselves only contribute to minor olefin oxidation sideways. However, the oxomanganese(IV) species were found to perform the Lewis acid activation of the acyl and alkyl hydroperoxides or iodosylarenes to form the new type of oxidant [oxomanganese(IV) complex with a terminal oxidant], with the latter accounting for the predominant enantioselective epoxidation pathway in the nonheme manganese-catalyzed olefin epoxidations.