The epoxidation process of semi-synthetic triterpenoids 2-methyl-3-oxo-19β,28-epoxy- 18α-olean-1-ene, and its allylic alcohol derivatives were examined. 1,2α-epoxide, as the main product, was found to be formed from the starting enone exposed to m-chloroperbenzoic acid (mCPBA). In the case of hydroxy-directed mCPBA-oxidation of triterpenic allyl alcohols and their 3α-alkyl-substituted derivatives, inversion of C1 and C2 asymmetric centers with the formation of 1,2β-epoxyalcohols took place. The synthesis of 2,3α-epoxides was fulfilled from 2,3-dialkyl-substituted C(3) allyl alcohols by the action of pyridinium chlorochromate under [1,3]-oxidative rearrangement conditions. The transformations brought about enabled chiral oleanane derivatives with an oxygen-containing substituent at the C1, C2, and C3 atoms to be obtained. The study also provides information on in silico PASS prediction of pharmacological effects and in vitro evaluation of the cytotoxic activity of the synthesized compounds.