a-Substituted heterocycles like benzopyrans, tetrahydropyrans, tetrahydrofurans, tetrahydroisoquinolines,tetrahydroquinolines, and piperidines, represent ubiquitous structural motifs in numerous alkaloids exhibiting a wide range of pharmacological activities.Direct C-H functionalization of the heterocycles with a variety of carbon nucleophiles presents an atom-economic protocol without prior installation of activating groups, and is therefore attractive.While a number of different approaches have been established, the catalytic asymmetric variants have not been well explored.Our research mainly focused on the development of the enantioselective oxidative C-H functionalization of a series of heterocycles and the applications in natural product synthesis, and the discovery of biologically interesting small molecules.