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. The 1H and 31P NMR studies of the reaction of Ru(CO)(PPh3)3 with o-aryloxy pivalophenone revealed that the C-H bond cleavage is a kinetically favorable process but the C-O bond cleavage is a thermodynamic one. The reaction of 2'-methoxyacetophenone with vinylsilane and organoboronate resulted in chemoselective C-C bond formation.
Ueno
Satoshi
S
Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan.
Mizushima
Eiichiro
E
Chatani
Naoto
N
Kakiuchi
Fumitoshi
F
D002244:Carbon / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004952:Esters / Q000737:chemistry; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
D004952:Esters; D007659:Ketones; D009942:Organometallic Compounds; D002244:Carbon; D012428:Ruthenium; D010100:Oxygen