Enantioselective Synthesis of Homoallylic Azides and Nitriles via Palladium-Catalyzed Decarboxylative Allylation

Azides
and nitriles are important building blocks for the synthesis
of nitrogen-containing bioactive compounds. The first example of enantioselective
palladium-catalyzed decarboxylative allylation of α-azido and
cyano β-ketoesters is reported. Indanone derivatives were obtained
in 50–88% yield/77–97% ee and 46–98% yield/78–93%
ee for azide and nitrile substituents, respectively. The required
starting materials were synthesized in one step from ketoesters via
electrophilic azidation and cyanation using benziodoxole hypervalent
iodine reagents. The products could be easily converted into useful
nitrogen-containing building blocks, such as triazoles, amides, or
α- and β- amino ketones.