Rh(II)-Catalyzed Selective C(sp)-H Bond Electrophilic Amination of Aryl Azide-Tethered 1,3-Dicarbonyl Compounds.

Herein, we report the accomplishment of Rh(II)-catalyzed intramolecular amination of aryl azide-tethered 1,3-dicarbonyls to access privileged heterocyclic scaffolds with exclusive diastereoselectivity under simple reaction conditions. This method also allows an unconventional direct α-amination at electron-deficient C(sp)-H bonds of aryl azide-tethered 1,3-diketones to afford fused 2-azatricyclo[4.4.