title: Palladium-catalyzed amination of aryl chlorides and bromides with ammonium salts.
abstract: We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Rebecca A
authors.initials: RA
authors.lastname: Green
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D000586:Amination; D000588:Amines / Q000737:chemistry; D000641:Ammonia / Q000737:chemistry; D000814:Aniline Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D012492:Salts
chemical_list: D000588:Amines; D000814:Aniline Compounds; D006842:Hydrocarbons, Brominated; D006843:Hydrocarbons, Chlorinated; D012492:Salts; D010165:Palladium; D000641:Ammonia