Investigations in the Transition Metal Catalyzed Aziridination of Olefins, Amination, and Other Insertion Reactions with Bromamine-T as the Source of Nitrene

Abstract

Investigations into the transition metal catalyzed aziridination of olefins with Bromamine-T as a new source of nitrene is presented in this account. Comparison of Chloramine-T and Bromamine-T in this reaction indicates that the latter is superior as the source of nitrene. Systematic study with several transition metal based catalysts suggests that Cu-halides are the best catalysts. A first report of aziridination under microwave and ultrasound irradiation conditions is also presented. Copper-catalyzed aziridination of methyl cinnamate with Bromamine-T did not proceed at ambient temperature but was effected smoothly under ultrasound irradiation to furnish trans-aziridine selectively, while under microwave irradiation, a mixture of cis and trans isomers, was obtained. It has been demonstrated that aziridination of olefins proceeds smoothly with inexpensive bleaching powder. Preliminary results of Rh-catalyzed benzylic insertion reactions with Bromamine-T are included in this account.