RESUMO
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.
RESUMO
Herein we have reported the palladium(0)-catalyzed decarboxylative oxa-Michael addition/remote α-allylation/1,3- migration of prochiral allyl carbonate-tethered cyclohexadienones in good yields. This unconventional intramolecular rearrangement is triggered by the base-mediated retro-Michael ring-opening reaction (ß-elimination) and subsequent syn-selective oxa-Michael addition on the less substituted enone functionality. The generality of tandem decarboxylative allylation was examined with various substrates and in the gram-scale reaction.
