SN2 Reaction versus Electron Transfer in the Oxygen Transfer by Dimethyldioxirane to Nitrogen Heteroarenes

Abstract

The rates of the N oxidation of aromatic amines with dimethyldioxirane (DMD) have been compared with those of the methylation of the same compounds with methyl iodide, and an excellent correlation (r = 0.977) for the log k values was obtained. The correlation with the ionization potentials was significantly worse. Thus, the N oxidation with DMD proceeds through an SN2 rather than an electron transfer (ET) mechanism [Eq. (a)].