Tuning Donor Ability of Oxygen with Inverse α-Effect: Two Levels of Kinetic Control Open Access to Four Classes of Peroxygenated Heterocycles

Abstract

Tunable acid-catalyzed reaction with hydrogen peroxide open access to diverse oxygen-rich cyclic peroxides from common 1,4-diketone precursors. Precise kinetic control via acid and hydrogen peroxide loadings selectively channels the reaction along distinct mechanistic pathways, leading to ozonides, tetraoxanes, 1,2-dioxanes, or dihydroperoxyfurans, all obtained in good yields. The gatekeepers of these pathways are key cationic intermediates, with stereoelectronic effects playing a central role in determining product distribution. This mechanistic feature offers versatile entry to structurally diverse peroxides from a single precursor.