Formation of singlet oxygen in the deoxygenation of heteroarene N-oxides by dimethyldioxirane

Abstract

4-Dimethylaminopyridine-N-oxid 2 and 2′,3′,5′-triacetyladenosine-N¹-oxide 4 are partially deoxygenated by dimethyldioxirane (DMD) to the corresponding amines 1 and 3; the formation of singlet oxygen suggests a polar rather than a radical mechanism, in which we propose S_N2 attack of the N-oxide on the dioxirane peroxide bond.