A facile and efficient asymmetric dearomative oxyalkylation of indoles with TEMPO oxoammonium salt and a variety of aldehydes and ketones has been described. This metal-free approach provides a straightforward access to C2 quaternary oxindoles in high yields with excellent diastereoand enantioselectivities under very mild conditions. The reaction goes smoothly even with only 0.1% equivalent catalyst. Moreover, 2-alkylindoles have proven to be suitable substrates for the first time.

The first organocatalytic enantioselective oxidative C-H functionalization of N-acyl tetrahydroisoquinolines with vinyl and aryl boronates promoted by a chiral Brønsted acid is described. This metal-free process tolerates a wide range of electronically varied N-acyl tetrahydroisoquinolines and structurally diverse boronates with good to excellent enantioselectivities.

The first organocatalytic enantioselective C-H alkenylation and arylation reactions of N-carbamoyl tetrahydropyridines and tetrahydro-β-carbolines (THCs) are described. The metal-free processes represent an efficient and straightforward approach to a variety of structurally and electronically diverse α-substituted tetrahydropyridines and THCs in good yields with excellent regio- and enantioselectivities. Preliminary control experiments provide important insights into the reaction mechanism.

A manganese dioxide (MnO2)-methanesulfonic acid (CH3SO3H) oxidation system has been developed to efficiently promote direct coupling of benzylic ethers and carbamates with simple ketones via oxidative C-H bond activation. The alkylation proceeds smoothly under air atmosphere to afford the corresponding products in good to excellent yields (53-87%). The employment of the combination of MnO2 and CH3SO3H is attractive on the basis of economical and environmental issues.