Direct amination of olefins through sequential triazolinedione ene reaction and carbanion-assisted cleavage of the N-N urazole bond

Allylic amines 5 are obtained in 30-55% overall yields by the base catalyzed hydrolysis of trialkylated allylic urazoles 3; the latter are prepared by the TAD ene reaction of the appropriate olefin and further N-alkylation with alpha-bromoacetophenone. The proposed mechanism for this novel urazole rupture is based on the generation of a carbanion adjacent to the hydrazide functionality, which induces urazole ring-opening by cleavage of the N-N bond.