Rh₂(II)-Catalyzed Selective Aminomethylene Migration from Styryl Azides

Rh₂(II)-Carboxylate complexes were discovered to promote the selective migration of aminomethylenes in β,β-disubstituted styryl azides to form 2,3-disubstituted indoles. Mechanistic data are also presented that suggest that the migration occurs stepwise before diffusion of the iminium ion.