Tert-Butyldiazene oxide as a leaving group

Abstract

Diazene oxides can be prepared from almost any nitrogen-containing functional group, but the reverse reactions are limited primarily to oxidation and reduction reactions. The synthetic potential of diazene oxides containing substituents has been largely unexplored [1, 2]. We have found that the tert-butyldiazene oxide group in activated positions of pyridine (Ia-c) and quinoxaline (Id) readily undergoes nucleophilic substitution upon reaction with amines. For example, reaction with ammonia results in the formation of heterocyclic amines IIa-d and tert-butyldiazotate III, which is unstable: