Palladium-catalyzed coupling of arylamines and 2-bromo-3,3,3-trifluoropropene (BTP) was investigated. When a toluene solution of aniline and BTP was heated at 110 degrees C in the presence of Pd-2(dba)(3)center dot CHCl3, 1,1'-diphenylphosphinoferrocene and CS2CO3 under an argon atmosphere, N-(1,1,1-trifluoro-2-propylidene)aniline was obtained in excellent GC and F-19 NMR yields (99%) and isolated yield (92%). CS2CO3 was exclusively effective in the coupling reaction among the bases tested. The coupling using 2-aminobenzonitriles as substrates provided not only 2-N-(1,1,1-trifluoro-2-propylidene)aminobenzonitriles but also 4-amino-2-trifluoromethylquinolines and 2-trifluoromethyl-4-N-(1,1,1-trifluoro-2-propylidene)aminoquinolines. The strong electron-withdrawing character of CF3 will enhance the acidity of the methyl proton in the N-(1,1,1-trifluoromethyl-2-propylidene)an-no group, resulting in the attack of the methyl proton to the carbon in the cyano group to give 4-amino-2-trifluoromethylquinolines. Moreover, the one-pot synthesis of 2-trifluoromethylindoles with 2-bromoanilines and BTP was achieved by use of Pd(OAc)(2), 2-dicyclohexylphosphino-2,4',6'-triisopropylbipenyl and CS2CO3. The Pd-catalyzed intramolecular Heck coupling of the vinyl group in 2-bromo-N-(1-trifluoromethyl)vinylanilines, which is the tautmeric isomer of 2-bromo-N-(1,1,1-tfifluoro-2-propylidene)anilines, and the C-Br bond presumably furnished indole rings. The C-N double bond of N-(1,1,1-trifluoro-2-propylidene) amino group obtained here was smoothly hydrogenated to N-(1-methyl-2,2,2-trifluoro)ethyl amino group using LiAlH4 or H-2 with Pd/C. (C) 2007 Elsevier B.V. All rights reserved.