1170176-97-2Relevant academic research and scientific papers
Palladium-Catalyzed Electrochemical C-H Alkylation of Arenes
Yang, Qi-Liang,Li, Chuan-Zeng,Zhang, Liang-Wei,Li, Yu-Yan,Tong, Xiaofeng,Wu, Xin-Yan,Mei, Tian-Sheng
supporting information, p. 1208 - 1212 (2018/10/20)
Palladium-catalyzed electrochemical C-H functionalization reactions have emerged as attractive tools for organic synthesis. This process offers an alternative to conventional methods that require harsh chemical oxidants. However, this electrolysis requires divided cells to avoid catalyst deactivation by cathodic reduction. Herein, we report the first example of palladium-catalyzed electrochemical C-H alkylation of arenes using undivided electrochemical cells in water, thereby providing a practical solution for the introduction of alkyl groups into arenes.
On the mechanism of palladium-catalyzed aromatic C-H oxidation
Powers, David C.,Xiao, Daphne Y.,Geibel, Matthias A. L.,Ritter, Tobias
supporting information; experimental part, p. 14530 - 14536 (2010/12/18)
The mechanism of Pd-catalyzed aromatic C-H oxidation chemistry continues to be vigorously discussed. Historically, Pd(II)/Pd(IV) catalysis cycles have been proposed. Herein, we present a detailed study of Pd(OAc)2-catalyzed aromatic C-H chlorination and propose dinuclear Pd(III) complexes as intermediates. We have identified a succinate-bridged dinuclear Pd(II) complex, which self-assembles during catalysis, as the catalyst resting state. In situ monitoring of catalysis has revealed that chlorination proceeds with turnover-limiting oxidation of a dinuclear resting state, and that acetate ions, liberated during the formation of the catalyst resting state, catalyze the bimetallic oxidation. Informed by reaction kinetics analysis, relevant dinuclear Pd(III) complexes have been prepared and observed to undergo selective C-Cl reductive elimination. Based on the combination of kinetic data obtained during catalysis and explicit structural information of relevant intermediates, we propose a Pd(II)2/Pd(III)2 catalysis cycle for Pd(OAc)2-catalyzed aromatic C-H chlorination.
Bimetallic palladium catalysis: Direct observation of Pd(III)-Pd(III) intermediates
Powers, David C.,Geibel, Matthias A. L.,Klein, Johannes E. M. N.,Ritter, Tobias
supporting information; experimental part, p. 17050 - 17051 (2010/03/25)
(Chemical Equation Presented) PhI(OAc)2 is a common oxidant for Pd-catalyzed C-H bond functionalizations. Mechanistic hypotheses since the 1960s have suggested a Pd(II)/Pd(IV) mechanism. Here we present evidence for the relevance of bimetallic Pd(III) complexes to catalysis. A bimetallic Pd(III) acetate was isolated and can afford product by bimetallic reductive elimination.
