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

Satoshi Ueno, Eiichiro Mizushima, Naoto Chatani, Fumitoshi Kakiuchi

Research output: Contribution to journalArticle

129 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)16516-16517
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number51
DOIs
Publication statusPublished - 2006 Dec 27

Fingerprint

Ruthenium
Carbon Monoxide
Hydrogen
Hydrogen bonds
Carbon
Nuclear magnetic resonance
Observation
Oxygen
Thermodynamics
Catalyst activity
X-Rays
X rays
Proton Magnetic Resonance Spectroscopy
benzeneboronic acid
2'-methoxyacetophenone
vinylsilane

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{a14b9a467d0e4082a054d93af2ee73e1,
title = "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",
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.",
author = "Satoshi Ueno and Eiichiro Mizushima and Naoto Chatani and Fumitoshi Kakiuchi",
year = "2006",
month = "12",
day = "27",
doi = "10.1021/ja067612p",
language = "English",
volume = "128",
pages = "16516--16517",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "51",

}

TY - JOUR

T1 - 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

AU - Ueno, Satoshi

AU - Mizushima, Eiichiro

AU - Chatani, Naoto

AU - Kakiuchi, Fumitoshi

PY - 2006/12/27

Y1 - 2006/12/27

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=33845946746&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845946746&partnerID=8YFLogxK

U2 - 10.1021/ja067612p

DO - 10.1021/ja067612p

M3 - Article

C2 - 17177397

AN - SCOPUS:33845946746

VL - 128

SP - 16516

EP - 16517

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 51

ER -