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, 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.

Ruthenium-catalyzed amino- and alkoxycarbonylations with carbamoyl chlorides and alkyl chloroformates via aromatic C-H bond cleavage.

Ruthenium-catalyzed regioselective direct amino- and alkoxycarbonylations of aromatic rings via C-H bond cleavage using chlorocarbonyl compounds are described. A broad generality of amide and ester groups was achieved taking advantage of the wide availability of carbonylating agents. Alkyl chloroformates, inapplicable to usual Friedel-Crafts methods, can also be used for direct catalytic alkoxycarbonylation.

Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds.

When RuH2(CO)(PPh3)3 was reacted with 2,2-dimethyl-1-(2-p-tolylphenyl)propan-1-one (2), the ruthenium-aryloxy complex 3 was obtained in 76% yield. The structure of this complex was determined from 1H and 31P NMR and X-ray data. Complex 3 showed the catalytic activity for the coupling of 2 with the phenylboronate 4.

Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage.

Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively.

Au(I)-catalyzed highly efficient intermolecular hydroamination of alkynes.

[reaction: see text] Addition of aniline derivatives to aromatic and aliphatic alkynes proceeds efficiently in the presence of a gold(I) catalyst (0.01-1.0 mol %) to afford ketimines in good yields