157557-78-3Relevant articles and documents
Catalytic Addition of Aromatic Carbon-Hydrogen Bonds to Olefins with the Aid of Ruthenium Complexes
Kachiuchi, Fumitoshi,Sekine, Shinya,Tanaka, Yasuo,Kamatani, Asayuki,Sonoda, Motohiro,et al.
, p. 62 - 83 (1995)
Ruthenium complexes, e.g., Ru(H)2(CO)(PPh3)3, have been found to catalyze the addition of ortho C-H bonds of aromatic ketones to olefins to give 1:1 coupling products in good to excellent yields.The C-C bond formation takes place exclusively at the terminal carbon atom of olefins except for styrene which affords a mixture of two regioisomers.Acetylnaphthalenes, cyclic aromatic ketones, and heteroaromatic ketones also react with triethoxyvinylsilane to give 1:1 addition products in virtually quantitative yields.From 2'-acetonaphthone or 3-acetylthiophene, in which two different reaction sites are available, only one out of four possible regioisomers is obtained.The importance of the coordination of the oxygen atom of the ketone to ruthenium and the intervention of a cyclometallation intermediate are suggested.A deuterium labeling experiment using acetophenone-d5 and triethoxyvinylsilane shows that an H/D exchange between the aromatic and olefinic positions takes place to some extent, even prior to the formation of the product.This implies that the rate-determining step is not the C-H bond cleavage step, but the product forming step.
Ruthenium chloride as an efficient catalytic precursor for hydroarylation reactions via C-H bond activation
Simon, Marc-Olivier,Genet, Jean-Pierre,Darses, Sylvain
supporting information; experimental part, p. 3038 - 3041 (2010/08/20)
A very simple and efficient catalytic system for the hydroarylation of olefins by aromatic ketones and Michael acceptors using simple and inexpensive ruthenium trichloride as a ruthenium source is described. These very mild conditions (dioxane at 80 -°C)
C-C bond formation via C-H bond activation using an in situ-generated ruthenium catalyst
Martinez, Remi,Simon, Marc-Olivier,Chevalier, Reynald,Pautigny, Cyrielle,Genet, Jean-Pierre,Darses, Sylvain
supporting information; experimental part, p. 7887 - 7895 (2009/10/17)
We report here our full results concerning the possibility of generatingin situ from a stable and readily available ruthenium(II) source a high ly active ruthenium catalyst for C-H bond activation. The versatility ofthis catalytic system has been demonstrated, as it offers the possibili ty of modifying the electronic and steric properties of the catalyst by fine-tuning of the ligands, allowing functionalization of various substrates. Aromatic ketones and imines could be easily functionalized by the reaction with either vinylsilanes or styrenes, depending on the electronic and steric nature of the ligand. Moreover, variable-temperature NMR experiments and the isolation of a ruthenium intermediate complex provided some insights into the generation of the active catalytic ruthenium species in this reaction.
