title: Opening the Way to Catalytic Aminopalladation/Proxicyclic Dehydropalladation: Access to Methylidene γ-Lactams.
abstract: A new aerobic intramolecular palladium(II)-based catalytic system that triggers aminopalladation/dehydropalladation of N-sulfonylalkenylamides to give the corresponding methylidene γ-lactams has been identified. Use of triphenylphosphine and chloride anion as ligands is mandatory for optimal yields, and molecular oxygen can be used as the sole terminal oxidant. Scope and limitations of the methods are described. A mechanism is proposed on the basis of experimental results as well as density functional theory calculations.
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Mélanie M
authors.initials: MM
authors.lastname: Lorion
authors.affiliation: Centro de Química e Bioquímica, DQB, Faculdade de Ciências, Universidade de Lisboa , 1749-016 Lisboa, Portugal.
authors.forename: Filipe J S
authors.initials: FJ
authors.lastname: Duarte
authors.affiliation: Centro de Química e Bioquímica, DQB, Faculdade de Ciências, Universidade de Lisboa , 1749-016 Lisboa, Portugal.
authors.forename: Maria José
authors.initials: MJ
authors.lastname: Calhorda
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Julie
authors.initials: J
authors.lastname: Oble
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu, 75252 Paris Cedex 05, France.
authors.forename: Giovanni
authors.initials: G
authors.lastname: Poli
mesh_terms: D002384:Catalysis; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D016877:Oxidants / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D007769:Lactams; D016877:Oxidants; D010165:Palladium; D010100:Oxygen