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.

Palladium(0)-Catalyzed Remote Decarboxylative Allylation and Base-Mediated 1,3-Migration.

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 (β-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.

Enantioselective Desymmetrization of Prochiral Cyclopentene-1,3-diones Triggered by Remote C(sp)-N Bond Formation.

The enantioselective desymmetrization via remote C(sp)-H amidation of the prochiral 2,2-disubstituted cyclopentene-1,3-dione with -methoxybenzamide has been developed. The overall process was catalyzed by a chiral bifunctional thiourea catalyst through a sequential conjugate-addition-elimination-tautomerization. This strategy provides rapid access to highly functionalized five-membered carbocycles, bearing an all-carbon quaternary stereogenic center through remote stereocontrol in high yields with moderate to excellent enantioselectivities.