Direct amination of olefins through sequential triazolinedione ene reaction and carbanion-assisted cleavage of the N-N urazole bond
[formula: see text] 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.
Adam
W
Institute of Organic Chemistry, University of Wurzburg, Germany. adam@chemie.uni-wuerzburg.de
Pastor
A
Wirth
T