- Palladium-Catalyzed Ring-Forming Aminoalkenylation of Alkenes with Aldehydes Initiated by Intramolecular Aminopalladation
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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.
- Hu, Yue,Xie, Yinjun,Shen, Zhiqiang,Huang, Hanmin
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supporting information
p. 2473 - 2477
(2017/02/23)
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- Palladium-catalyzed highly selective ortho-halogenation (I, Br, Cl) of arylnitriles via sp2 C-H bond activation using cyano as directing group
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A palladium-catalyzed ortho-halogenation (I, Br, Cl) of arylnitrile is described. The optimal reaction conditions were identified after examining various factors such as catalyst, additive, solvent, and reaction temperature. Using cyano as the directing group, the halogenation reaction gave good to excellent yields. The method is compatible to the arylnitriles with either electron-withdrawing or electron-donating groups. The reaction is available to the substrate in at least gram scale. The present method was successfully applied to the synthesis of the precursors of paucifloral F and isopaucifloral F.
- Du, Bingnan,Jiang, Xiaoqing,Sun, Peipei
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p. 2786 - 2791
(2013/04/24)
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