Tuning the donor ability of oxygen with the inverse α-effect: two levels of kinetic control open access to four classes of peroxygenated heterocycles

Abstract

A tunable acid-catalyzed reaction with hydrogen peroxide opens 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 a versatile route to structurally diverse peroxides from a single precursor.