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Palladium‐Catalyzed Ring‐Forming Aminoalkenylation of Alkenes with Aldehydes Initiated by Intramolecular Aminopalladation
Author(s) -
Hu Yue,
Xie Yinjun,
Shen Zhiqiang,
Huang Hanmin
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201611853
Subject(s) - nucleophile , chemistry , palladium , intramolecular force , catalysis , selectivity , ring (chemistry) , hydride , combinatorial chemistry , nucleophilic addition , photochemistry , medicinal chemistry , organic chemistry , metal
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 Csp 3 −Pd species was controlled by the confined conformation and the nucleophilicity of the Csp 3 −Pd bond was enhanced by the strong electron‐donating effect of the nitrogen atom.