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

J Am Chem Soc. 2006 Dec 27;128(51):16516-7. doi: 10.1021/ja067612p.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon / chemistry*
  • Crystallography, X-Ray
  • Esters / chemistry
  • Hydrogen Bonding
  • Ketones / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds* / chemical synthesis
  • Organometallic Compounds* / chemistry
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Ruthenium / chemistry*
  • Stereoisomerism

Substances

  • Esters
  • Ketones
  • Organometallic Compounds
  • Carbon
  • Ruthenium
  • Oxygen