These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • 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.
    Author: Kakiuchi F, Kochi T, Mizushima E, Murai S.
    Journal: J Am Chem Soc; 2010 Dec 22; 132(50):17741-50. PubMed ID: 21114294.
    Abstract:
    Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH(2)(CO)(PPh(3))(3), with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C(6)H(4)PPh(2))(H)(CO)(PPh(3))(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. (1)H and (31)P 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(6)H(4)C(O)Me))(H)(CO)(PPh(3))(2), participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d(5) 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.
    [Abstract] [Full Text] [Related] [New Search]