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

Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH2(CO)(PPh3)(3), with trimethylvinylsilane at 90 degrees C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C6H4PPh2)(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. H-1 and P-31 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'-MeC6H4C-(O)Me))(H)(CO)(PPh3)(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.