95607-03-7Relevant articles and documents
Tuning the Selectivity of Palladium Catalysts for Hydroformylation and Semihydrogenation of Alkynes: Experimental and Mechanistic Studies
Beller, Matthias,Ge, Yao,Jackstell, Ralf,Jiao, Haijun,Liu, Jiawang,Wei, Duo,Wei, Zhihong,Yang, Ji
, p. 12167 - 12181 (2020/11/27)
Here, we describe a selective palladium catalyst system for chemodivergent functionalization of alkynes with syngas. In the presence of an advanced ligand L2 bearing 2-pyridyl substituent as a built-in base, either hydroformylation or semihydrogenation of diverse alkynes occurs with high chemo- and stereoselectivity under comparable conditions. Mechanistic studies, including density functional theory (DFT) calculations, kinetic analysis, and control experiments, revealed that the strength and concentration of acidic cocatalysts play a decisive role in controlling the chemoselectivity. DFT studies disclosed that ligand L2 not only promotes heterolytic activation of hydrogen similar to frustrated Lewis pair (FLP) systems in the hydrogenolysis step for hydroformylation but also suppresses CO coordination to promote semihydrogenation under strong acid conditions. This switchable selectivity provides a strategy to design new catalysts for desired products.
N-Allylation of Imides Catalyzed by Palladium(0)
Inoue, Yoshio,Taguchi, Masaaki,Toyofuku, Masanori,Hashimoto, Harukichi
, p. 3021 - 3022 (2007/10/02)
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