Ruthenium-Catalyzed Addition of Carbon-Hydrogen Bonds in Aromatic Ketones to Olefins. The Effect of Various Substituents at the Aromatic Ring

Motohiro Sonoda, Fumitoshi Kakiuchi, Naoto Chatani, Shinji Murai

Research output: Contribution to journalArticle

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Abstract

To obtain further insight into the new ruthenium-catalyzed reaction of carbon-hydrogen bonds in aromatic ketones with olefins, the effect of various substituents at the aromatic ring is examined. Reaction of o-methylacetophenone with triethoxyvinylsilane (2) in the presence of [Ru(H)2(CO)(PPh3)3] (3)as the catalyst gave the 1 : 1 addition product in quantitative yield. Similarly, the ketone having an o-CF3 group gave the coupling product 9 in 92% yield. However, ortho substituents such as OMe, F, and CN, seem to react with and kill the catalyst so that no efficient reaction was attained. In the cases of the reactions of p-methoxy- and p-fluoroacetophenones with 2, the corresponding 1 : 2 addition products were obtained as the major product. In the cases of m-substituted acetophenones, two different C-H bonds at the ortho positions are available. The C-C bond formation preferentially occurred at the sterically less congested positions. Exceptions are the reactions of m-methoxy- and m-fluoroacetophenones, in which the C-C bond formation took place preferentially at the more congested position. This may be due to the coordination of oxygen or fluorine atom to ruthenium. The factors controlling these selectivities are discussed.

LanguageEnglish
Pages3117-3128
Number of pages12
JournalBulletin of the Chemical Society of Japan
Volume70
Issue number12
Publication statusPublished - 1997 Dec
Externally publishedYes

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Ruthenium
Alkenes
Ketones
Hydrogen bonds
Acetophenones
Carbon
Catalysts
Fluorine
Carbon Monoxide
Oxygen
Atoms
vinyltriethoxysilane

ASJC Scopus subject areas

  • Chemistry(all)

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Ruthenium-Catalyzed Addition of Carbon-Hydrogen Bonds in Aromatic Ketones to Olefins. The Effect of Various Substituents at the Aromatic Ring. / Sonoda, Motohiro; Kakiuchi, Fumitoshi; Chatani, Naoto; Murai, Shinji.

In: Bulletin of the Chemical Society of Japan, Vol. 70, No. 12, 12.1997, p. 3117-3128.

Research output: Contribution to journalArticle

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abstract = "To obtain further insight into the new ruthenium-catalyzed reaction of carbon-hydrogen bonds in aromatic ketones with olefins, the effect of various substituents at the aromatic ring is examined. Reaction of o-methylacetophenone with triethoxyvinylsilane (2) in the presence of [Ru(H)2(CO)(PPh3)3] (3)as the catalyst gave the 1 : 1 addition product in quantitative yield. Similarly, the ketone having an o-CF3 group gave the coupling product 9 in 92{\%} yield. However, ortho substituents such as OMe, F, and CN, seem to react with and kill the catalyst so that no efficient reaction was attained. In the cases of the reactions of p-methoxy- and p-fluoroacetophenones with 2, the corresponding 1 : 2 addition products were obtained as the major product. In the cases of m-substituted acetophenones, two different C-H bonds at the ortho positions are available. The C-C bond formation preferentially occurred at the sterically less congested positions. Exceptions are the reactions of m-methoxy- and m-fluoroacetophenones, in which the C-C bond formation took place preferentially at the more congested position. This may be due to the coordination of oxygen or fluorine atom to ruthenium. The factors controlling these selectivities are discussed.",
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