The allylic azide rearrangement: achieving selectivity.
Allylic azides undergo a rapid [3.3]-sigmatropic rearrangement which results in dynamic equilibrium of several isomers. Thus, reactions of allylic azides usually result in mixtures of products. However, even small differences in reactivity of the isomeric allylic azides can be amplified to result in a single product in good to excellent yields. For example, the Cu(I)-catalyzed cycloaddition with alkynes selectively captures primary and secondary allylic azide isomers, whereas MCPBA epoxidation favors isomers which contain more electron-rich double olefins.
Feldman
Alina K
AK
Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, La Jolla, California 92037, USA.
Colasson
Benoît
B
Sharpless
K Barry
KB
Fokin
Valery V
VV
D001386:Azides / Q000737:chemistry*; D002384:Catalysis
D001386:Azides