Tropene Derivatives by Sequential Intermolecular and Transannular, Intramolecular Palladium-Catalyzed Hydroamination of Cycloheptatriene

• Published in: Journal of the American Chemical Society Vol. 128; no. 25; pp. 8134 - 8135
• Main Authors: Sakai, Norio, Ridder, André, Hartwig, John F
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 28.06.2006; Amer Chemical Soc
• Subjects: Amination; Catalysis; Chemistry; Chemistry, Multidisciplinary; Cyclization; Cycloheptanes - chemistry; Exact sciences and technology; Kinetics and mechanisms; Molecular Structure; Organic chemistry; Palladium - chemistry; Physical Sciences; Polyenes - chemistry; Reactivity and mechanisms; Science & Technology; TRANSPORTER; ACID; ENANTIOSELECTIVE SYNTHESIS; LIGANDS; 1,3-DIENES; ANALOGS; SCOPE; BITE ANGLE; TROPANES; BINDING; Intramolecular reaction; Catalytic reaction; Trienic compound; Nitrogen heterocycle; Palladium Complexes; Transition metal Complexes; Experimental study; Bicyclic compound; Reaction mechanism; Transannular reaction; Platinoid Complexes; Catalyst activity; Monocyclic compound
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja061349a

A consecutive inter- and intramolecular hydroamination of cycloheptatriene with primary aromatic amines, benzylic amines, and β-phenethylamines occurs to produce pharmaceutically relevant tropene (8-azabicyclo[3.2.1]octene) frameworks in good to excellent yields. This reaction occurs in the presence of a catalyst generated from palladium trifluoroacetate, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene and a mild acid. Mechanistic studies reveal that the overall process has some reversible steps, but that the rate of these reverse reactions are far slower than the rates of the forward catalytic process.