Room-temperature regioselective c-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates

Fumitoshi Kakiuchi, Takuya Kochi, Eiichiro Mizushima, Shinji Murai

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Abstract

Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH 2(CO)(PPh3)3, with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C 6H4PPh2)(H)(CO)(PPh3)2, as a mixture of four geometric isomers. The activated complex showed high catalytic activity for C-H/olefin coupling, and the reaction of 2′-methylacetophenone with trimethylvinylsilane at room temperature for 48 h gave the corresponding ortho-alkylation product in 99% isolated yield. The activated catalyst was thermally robust and showed excellent catalytic activity under refluxing toluene conditions. 1H and 31P NMR studies of the C-H/olefin coupling at room temperature suggested that an ortho-ruthenated complex, P,P′-cis-C,H-cis-Ru(2′-(6′-MeC 6H4C(O)Me))(H)(CO)(PPh3)2, participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d5 indicated that the rate-limiting step was the C-C bond formation, not the C-H bond cleavage, and that each step prior to the reductive elimination was reversible. The rate of C-H/olefin coupling was found to exhibit pseudo first-order kinetics and to show first-order dependence on the ruthenium complex concentration.

Original languageEnglish
Pages (from-to)17741-17750
Number of pages10
JournalJournal of the American Chemical Society
Volume132
Issue number50
DOIs
Publication statusPublished - 2010 Dec 22

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Ruthenium
Alkenes
Ketones
Olefins
Carbon Monoxide
Ligands
Catalysts
Temperature
Catalyst activity
Isotope Labeling
Alkylation
Toluene
Isotopes
Isomers
Labeling
Nuclear magnetic resonance
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Room-temperature regioselective c-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates",
abstract = "Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH 2(CO)(PPh3)3, with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C 6H4PPh2)(H)(CO)(PPh3)2, as a mixture of four geometric isomers. The activated complex showed high catalytic activity for C-H/olefin coupling, and the reaction of 2′-methylacetophenone with trimethylvinylsilane at room temperature for 48 h gave the corresponding ortho-alkylation product in 99{\%} isolated yield. The activated catalyst was thermally robust and showed excellent catalytic activity under refluxing toluene conditions. 1H and 31P NMR studies of the C-H/olefin coupling at room temperature suggested that an ortho-ruthenated complex, P,P′-cis-C,H-cis-Ru(2′-(6′-MeC 6H4C(O)Me))(H)(CO)(PPh3)2, participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d5 indicated that the rate-limiting step was the C-C bond formation, not the C-H bond cleavage, and that each step prior to the reductive elimination was reversible. The rate of C-H/olefin coupling was found to exhibit pseudo first-order kinetics and to show first-order dependence on the ruthenium complex concentration.",
author = "Fumitoshi Kakiuchi and Takuya Kochi and Eiichiro Mizushima and Shinji Murai",
year = "2010",
month = "12",
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language = "English",
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T1 - Room-temperature regioselective c-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates

AU - Kakiuchi, Fumitoshi

AU - Kochi, Takuya

AU - Mizushima, Eiichiro

AU - Murai, Shinji

PY - 2010/12/22

Y1 - 2010/12/22

N2 - Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH 2(CO)(PPh3)3, with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C 6H4PPh2)(H)(CO)(PPh3)2, as a mixture of four geometric isomers. The activated complex showed high catalytic activity for C-H/olefin coupling, and the reaction of 2′-methylacetophenone with trimethylvinylsilane at room temperature for 48 h gave the corresponding ortho-alkylation product in 99% isolated yield. The activated catalyst was thermally robust and showed excellent catalytic activity under refluxing toluene conditions. 1H and 31P NMR studies of the C-H/olefin coupling at room temperature suggested that an ortho-ruthenated complex, P,P′-cis-C,H-cis-Ru(2′-(6′-MeC 6H4C(O)Me))(H)(CO)(PPh3)2, participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d5 indicated that the rate-limiting step was the C-C bond formation, not the C-H bond cleavage, and that each step prior to the reductive elimination was reversible. The rate of C-H/olefin coupling was found to exhibit pseudo first-order kinetics and to show first-order dependence on the ruthenium complex concentration.

AB - Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH 2(CO)(PPh3)3, with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C 6H4PPh2)(H)(CO)(PPh3)2, as a mixture of four geometric isomers. The activated complex showed high catalytic activity for C-H/olefin coupling, and the reaction of 2′-methylacetophenone with trimethylvinylsilane at room temperature for 48 h gave the corresponding ortho-alkylation product in 99% isolated yield. The activated catalyst was thermally robust and showed excellent catalytic activity under refluxing toluene conditions. 1H and 31P NMR studies of the C-H/olefin coupling at room temperature suggested that an ortho-ruthenated complex, P,P′-cis-C,H-cis-Ru(2′-(6′-MeC 6H4C(O)Me))(H)(CO)(PPh3)2, participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d5 indicated that the rate-limiting step was the C-C bond formation, not the C-H bond cleavage, and that each step prior to the reductive elimination was reversible. The rate of C-H/olefin coupling was found to exhibit pseudo first-order kinetics and to show first-order dependence on the ruthenium complex concentration.

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