New chiral N-heterocyclic carbene (NHC) ligands have been developed and applied in the asymmetric Pd-catalyzed intramolecular a-arylation of amides producing 3,3-disubstituted-, spiro-, and aza-spirooxindoles in high yields (up to 99%) and excellent enantioselectivities (up to 97% ee). For the first time a palladacycle intermediates were isolated and fully characterized including X-ray crystal structure determinations. Analysis of these solid state structures demonstrates the importance of both the bulky tert-butyl groups and ortho-substituted aryl rings at the stereogenic centers of the ligand. Additionally, an extraordinarily efficient palladium-NHC catalyzed synthesis of highly enantioenriched 2,3-trans-fused indolines via asymmetric C(sp3)-H activation of an unactivated methylene unit was developed. It is noteworthy that this C-C coupling delivers the products with enantioselectivities of up to 95% ee despite the high temperature required. The initial results were extended to the synthesis of 2- and 2,3-disubstituted indolines. Racemic substrates reacted via highly asymmetric regiodivergent reactions.