title: C-H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas.
abstract: The dimeric cyclometalated complexes [Pd2{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}2(μ-Cl)2] (R = Me (1a), H (1b)) are prepared by reacting 1,1-dimethyl-3-phenylpropylammonium or 1-methyl-3-phenylpropylammonium triflate with Pd(OAc)2 in a 1:1 molar ratio and subsequent treatment with excess NaCl. The mononuclear derivatives [Pd{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}Cl(L)] (L = PPh3, R = Me (3a), H (3b); L = 4-picoline (4-pic), R = Me (4a), H (4b)) were prepared from 1a,b by splitting the chloro bridges with the neutral ligands L. A conformational analysis of the mononuclear palladacycles in solution has been carried out. Insertion of CO takes place into the Pd-C bond of complexes 1a,b, affording Pd(0) and the tetrahydro-benzazepinone 5a or 5b, which possesses potential pharmacological interest. Additionally, the triflate salt A or B undergoes catalytic carbonylation with CO to afford the corresponding N,N'-dialkylurea, using Pd(OAc)2/Cu(OAc)2, in boiling acetonitrile. The crystal structures of 3a·(1)/2H2O, 3b, 4b·CHCl3, and 5a were determined by X-ray diffraction studies.
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: Roberto
authors.initials: R
authors.lastname: Frutos-Pedreño
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: Eva
authors.initials: E
authors.lastname: García-Sánchez
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: María José
authors.initials: MJ
authors.lastname: Oliva-Madrid
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: Delia
authors.initials: D
authors.lastname: Bautista
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: Eloísa
authors.initials: E
authors.lastname: Martínez-Viviente
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: Isabel
authors.initials: I
authors.lastname: Saura-Llamas
authors.affiliation: Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, and ‡SAI, Universidad de Murcia , 3100 Murcia, Spain.
authors.forename: José
authors.initials: J
authors.lastname: Vicente