Rh 2 (II)-Catalyzed Selective C(sp 3 )-H Bond Electrophilic Amination of Aryl Azide-Tethered 1,3-Dicarbonyl Compounds.

Herein, we report the accomplishment of Rh 2 (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 3 )-H bonds of aryl azide-tethered 1,3-diketones to afford fused 2-azatricyclo[4.4.0.0 2,8 ]decanones and 2,2-disubstituted indolines, which are present in several biologically active alkaloids. Kinetic isotope experiments revealed that the nucleophilic addition of enol π-bonds on the transient electrophilic rhodium-nitrenoid intermediate enables C-N bond formation.