3-Alkyl/arylalkyl substituted 2-butenols 9, 10, 23a–d undergo regiospecific photooxygenation to furnish β-hydroxyhydroperoxides 11, 12, 24a–d, respectively, in reasonable yields. Acid catalyzed condensation of 11, 12, 24a–d with various ketones furnish new 1, 2, 4-trioxanes 13–18, 25a–d, 26a–d, 27a–d in good yields. Several of these trioxanes show promising antimalarial activity against multidrug-resistant Plasmodium ...