title: Palladium-Catalyzed Ring-Forming Aminoalkenylation of Alkenes with Aldehydes Initiated by Intramolecular Aminopalladation.
abstract: A palladium-catalyzed aminopalladation reaction followed by nucleophilic addition with aldehydes and dehydration is described. This direct and operationally simple procedure provides a rapid and reliable approach to a wide range of functionalized tetrahydroisoquinolines with high selectivity. Mechanistic studies disclosed that the nucleophilic addition, performed via a highly ordered transition-state, is the turnover-limiting step in which the inherent β-hydride elimination of the key Csp3-Pd species was controlled by the confined conformation and the nucleophilicity of the Csp3-Pd bond was enhanced by the strong electron-donating effect of the nitrogen atom.
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.|University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Hu
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.
authors.forename: Yinjun
authors.initials: Y
authors.lastname: Xie
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Shen
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.|Department of Chemistry, University of Science and Technology of China, Hefei, 230026, P. R. China.
authors.forename: Hanmin
authors.initials: H
authors.lastname: Huang
keywords: aminopalladation; nucleophilic addition; palladium; tandem reactions; β-hydride elimination