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The application of 3,5-bis(trifluoromethyl)phenylammonium triflate (BFPAT) as a convenient new organocatalyst for the synthesis of quinoxaline derivatives is described. In the presence of BFPAT, one-pot synthesis of a wide variety of quinoxaline derivatives was achieved by the reaction of various o-phenylenediamines and 1,2-dicarbonyl compounds in water.