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 °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. 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′-MeC6H4C(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, no...