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Preferred C2−H Activation of Quinoline N‐Oxides Catalyzed by Palladium Acetate: DFT Study on the Plausible Mechanism and Regioselectivity
Author(s) -
Zhang Lei,
Jiang Bo,
Zhou Jianguo,
Yu Lu,
Chen Yu
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201802749
Subject(s) - activation energy , quinoline , chemistry , regioselectivity , catalysis , density functional theory , activation barrier , kinetic energy , mechanism (biology) , palladium , reaction mechanism , stereochemistry , computational chemistry , organic chemistry , physics , quantum mechanics
A density functional theory study on the multi‐path and multi‐step C−H activation of quinoline N‐oxides catalyzed by the dimeric complex Pd 2 (OAc) 4 has been carried out to fully address the strong preference for C2−H activation observed experimentally. The plausible C−H activation mechanism was identified as the undirected mechanism rather than the coordination‐directed mechanism, because the former has lower free‐energy barriers than the latter. The kinetic and thermodynamic parameters of different C−H activation reactions have been calculated and compared. The preference for C2−H activation over C8−H activation should be a result of the kinetic discrimination, while that over the remaining C−H activation processes could be attributed to the thermodynamic spontaneity.