Cross-conjugated trienes are an exciting class of compounds that remain largely unexplored by the synthetic community. We have previously shown that cross-conjugated trienes can be obtained through an intramolecular rhodium(I)-catalyzed Alder-ene reaction in high yield. Our current efforts are aimed at exploring the reactivity of these scaffolds in the synthesis of natural products such as ovalicin and fumigillol. We have shown that treating triene A with a vanadium-catalyzed epoxidation protocol selectively produces bis-allylic epoxide B and progress of this diverging approach will be discussed.