A novel and selective synthesis of 2-indolyl-3oxoindolines or 2-(2-aminophenyl)quinolines through tunable dimerizations of 2-alkynylanilines is presented. Mechanistically, the formation of 2-indolyl-3-oxoindolines involves a Cu(OAc) 2 / O 2 -promoted intramolecular cyclization of 2-alkynylaniline to give the required indole and 3H-indol-3-one intermediates followed by the indolylation of 3H-indol-3-one. On the other hand, the formation of 2-(2-aminophenyl)quinolines is believed to go through a Bi(OTf) 3 /MesCO 2 H-catalyzed intermolecular N-nucleophilic addition between two 2-alkynylaniline molecules to give an enamine intermediate followed by its intramolecular C-nucleophilic addition/annulation. Notable features of these new methods include easily obtainable substrates, economical catalysts and oxidant, controllable selectivity, and high versatility toward diverse products.2,2-Disubstituted indolin-3-one constitutes the scaffold of numerous natural products such as Austamdine, Cephalinone, LipidGreen, Aristotelon, Isatisine A, and Halichrome A, 1 fluorescence probes, and solar-cell materials. 2 Among different kinds of 2,2-disubstituted indolin-3-one derivatives, 2-indolyl-3-oxoindolines are particularly attractive. This is because they not only have unique structural features but also demonstrate potent antiviral activities. 3 To date, several reliable methods for the preparation of 2-indolyl-3-oxoindolines have been reported by Ramana, Guchhait, Jiang, Liu, and many others. 4−6 In the past several years, we have developed some methods for the synthesis of biologically interesting heterocyclic compounds. 7 In this regard, we recently disclosed the synthesis of indolo[3,2-c]quinolines and 3-(2-aminophenyl)quinolines via [RhCp*Cl 2 ] 2 -catalyzed dimerization of 2-alkynylanilines under aerobic/anaerobic conditions (Schemes 1a and 1b). 7d In