Annulation Reactions of In-Situ-Generated N-(Het)aroyldiazenes with Isothiocyanates Leading to 2-Imino-1,3,4-oxadiazolines.

Abstract

A novel annulation reaction of N-(het)aroyldiazenes and isothiocyanates has been established. This transformation involves a sequential cyclization and desulfurization/intramolecular rearrangement to produce 2-imino-1,3,4-oxadiazolines. The less-stable N-(het)aroyldiazenes can be conveniently generated in situ by I2-mediated oxidation of hydrazides, which allows a one-pot synthesis of the products directly from readily accessible hydrazide and isothiocyanate substrates. This operationally simple synthetic process requires no use of malodorous isocyanides and can be conveniently conducted on a gram scale.