1 research outputs found
Rh<sub>2</sub>(II)-Catalyzed Selective C(sp<sup>3</sup>)–H Bond Electrophilic Amination of Aryl Azide-Tethered 1,3-Dicarbonyl Compounds
Herein,
we report the accomplishment of Rh2(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(sp3)–H
bonds of aryl azide-tethered 1,3-diketones to afford fused 2-azatricyclo[4.4.0.02,8]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