Metal-mediated Schmidt Reactions of Alkyl Azides with Alkenes and Alkynes

4 Metal-mediated Schmidt Reactions of Alkyl Azides with Alkenes and Alkynes 

The lack of regioselectivity, the limitation that tertiary or benzylic alcohols must be used as precursors to Schmidt reactions with carbocations, and the harsh Lewis acidic 

Toste and coworkers have shown that intramolecular Schmidt reactions of acetylenic azides were possible through Au(I) catalysis. Thus, treatment of a series of acetylenic azides with (dppm)Au2Cl2 provides pyrroles in good yields (Table 7.6). These reactions were tolerant of varying substitution and chemoselective when a 1,5-enyne was present, the desired cyclization still proceeded, albeit with reduced efficiency (entry 5). 

Johnston and coworkers have explored other dimensions of azide/enone reactivity. Thus, aziridines were obtained in moderate to excellent yields when acyclic enones were 

---