New stereospecific deamination of aziridines using dinitrogen tetroxide and t-butylthionitrite

Abstract

A new deamination reaction of aziridines using dinitrogen tetroxide and t-butylthionitrite under mild conditions was studied. The reaction of aziridines with dinitrogen tetroxide or t-butylthionitrite in dry acetonitrile or tetrahydrofuran was found to give the corresponding olefins stereospecifically in good yields. Dinitrogen Tetroxide has been known to be selfionized to $NO^+$ and $NO_3^-$ ion at low temperature in aprotic polar solvents, and is a good nitrosating reagent for thiols or amines. The reaction appears to proceed via the formation of N-nitrosoaziridine produced by nitrosation on the nitrogen atom of the aziridines. Since the sulfurnitrogen bond of t-butylthionitrite is relatively weaker than the oxygen-nitrogen bond of alkyl-nitrite, thionitrites are considered to be better deaminating reagent for aziridines. This reaction will be widely applicable to the synthesis of olefins.