The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane

Fumitoshi Kakiuchi, Mitsutaka Matsumoto, Kazuyuki Tsuchiya, Kimitaka Igi, Tomoo Hayamizu, Naoto Chatani, Shinji Murai

Research output: Contribution to journalArticle

107 Citations (Scopus)

Abstract

The Ru3(CO)12-catalyzed reaction of aromatic compounds such as arylazoles, arylimines, and arylpyridines with triethylsilane (2) gave silylation products in good to excellent yields. Amide and ester groups could also be used as a directing group. In nearly all cases, C-Si bond formation took place at a position ortho to the directing groups. This coupling reaction is tolerant of both electron-donating and -withdrawing groups such as methoxy, fluoro, and trifluoromethyl groups. We expected that the use of 2-naphthyl-3-methylpyridine would not result in the formation of a coupling product, because the severe steric repulsion between the methyl group and the peri-hydrogen at the 8-position would strongly inhibit the attainment of a co-planar geometry. Interestingly, however, the reaction of 2-naphthyl-3-methylpyridine afforded the corresponding silylation product in quantitative yield. This observation indicates that the formation of metalacycle intermediate is not essential for the catalytic reaction to proceed. When a deuterium-labeling experiment using phenyloxazoline-d5 was carried out in the absence of olefin, partial H/D scrambling occurred between the ortho positions of the phenyloxazoline and the Si-H of triethylsilane. This labeling experiment indicates that C-H bond cleavage is not the rate-determining step and that a rapid equilibrium prior to C-Si bond formation (i.e. the reductive elimination step) occurs in this catalytic reaction.

Original languageEnglish
Pages (from-to)134-144
Number of pages11
JournalJournal of Organometallic Chemistry
Volume686
Issue number1-2
DOIs
Publication statusPublished - 2003 Dec 1
Externally publishedYes

Fingerprint

Ruthenium
Labeling
ruthenium
Aromatic compounds
Deuterium
Alkenes
Carbon Monoxide
Amides
Olefins
Hydrogen
Esters
Experiments
Electrons
marking
Geometry
products
aromatic compounds
amides
alkenes
triethylsilane

Keywords

  • Aromatic C-H bonds
  • C-H bond cleavage
  • C-H/SiR coupling
  • Ruthenium catalysts
  • Triorganosilane

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane. / Kakiuchi, Fumitoshi; Matsumoto, Mitsutaka; Tsuchiya, Kazuyuki; Igi, Kimitaka; Hayamizu, Tomoo; Chatani, Naoto; Murai, Shinji.

In: Journal of Organometallic Chemistry, Vol. 686, No. 1-2, 01.12.2003, p. 134-144.

Research output: Contribution to journalArticle

Kakiuchi, F, Matsumoto, M, Tsuchiya, K, Igi, K, Hayamizu, T, Chatani, N & Murai, S 2003, 'The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane', Journal of Organometallic Chemistry, vol. 686, no. 1-2, pp. 134-144. https://doi.org/10.1016/S0022-328X(03)00448-0
Kakiuchi, Fumitoshi ; Matsumoto, Mitsutaka ; Tsuchiya, Kazuyuki ; Igi, Kimitaka ; Hayamizu, Tomoo ; Chatani, Naoto ; Murai, Shinji. / The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane. In: Journal of Organometallic Chemistry. 2003 ; Vol. 686, No. 1-2. pp. 134-144.
@article{6f1a53aec6d242d0bf8eb9984e9a98d0,
title = "The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane",
abstract = "The Ru3(CO)12-catalyzed reaction of aromatic compounds such as arylazoles, arylimines, and arylpyridines with triethylsilane (2) gave silylation products in good to excellent yields. Amide and ester groups could also be used as a directing group. In nearly all cases, C-Si bond formation took place at a position ortho to the directing groups. This coupling reaction is tolerant of both electron-donating and -withdrawing groups such as methoxy, fluoro, and trifluoromethyl groups. We expected that the use of 2-naphthyl-3-methylpyridine would not result in the formation of a coupling product, because the severe steric repulsion between the methyl group and the peri-hydrogen at the 8-position would strongly inhibit the attainment of a co-planar geometry. Interestingly, however, the reaction of 2-naphthyl-3-methylpyridine afforded the corresponding silylation product in quantitative yield. This observation indicates that the formation of metalacycle intermediate is not essential for the catalytic reaction to proceed. When a deuterium-labeling experiment using phenyloxazoline-d5 was carried out in the absence of olefin, partial H/D scrambling occurred between the ortho positions of the phenyloxazoline and the Si-H of triethylsilane. This labeling experiment indicates that C-H bond cleavage is not the rate-determining step and that a rapid equilibrium prior to C-Si bond formation (i.e. the reductive elimination step) occurs in this catalytic reaction.",
keywords = "Aromatic C-H bonds, C-H bond cleavage, C-H/SiR coupling, Ruthenium catalysts, Triorganosilane",
author = "Fumitoshi Kakiuchi and Mitsutaka Matsumoto and Kazuyuki Tsuchiya and Kimitaka Igi and Tomoo Hayamizu and Naoto Chatani and Shinji Murai",
year = "2003",
month = "12",
day = "1",
doi = "10.1016/S0022-328X(03)00448-0",
language = "English",
volume = "686",
pages = "134--144",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

T1 - The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane

AU - Kakiuchi, Fumitoshi

AU - Matsumoto, Mitsutaka

AU - Tsuchiya, Kazuyuki

AU - Igi, Kimitaka

AU - Hayamizu, Tomoo

AU - Chatani, Naoto

AU - Murai, Shinji

PY - 2003/12/1

Y1 - 2003/12/1

N2 - The Ru3(CO)12-catalyzed reaction of aromatic compounds such as arylazoles, arylimines, and arylpyridines with triethylsilane (2) gave silylation products in good to excellent yields. Amide and ester groups could also be used as a directing group. In nearly all cases, C-Si bond formation took place at a position ortho to the directing groups. This coupling reaction is tolerant of both electron-donating and -withdrawing groups such as methoxy, fluoro, and trifluoromethyl groups. We expected that the use of 2-naphthyl-3-methylpyridine would not result in the formation of a coupling product, because the severe steric repulsion between the methyl group and the peri-hydrogen at the 8-position would strongly inhibit the attainment of a co-planar geometry. Interestingly, however, the reaction of 2-naphthyl-3-methylpyridine afforded the corresponding silylation product in quantitative yield. This observation indicates that the formation of metalacycle intermediate is not essential for the catalytic reaction to proceed. When a deuterium-labeling experiment using phenyloxazoline-d5 was carried out in the absence of olefin, partial H/D scrambling occurred between the ortho positions of the phenyloxazoline and the Si-H of triethylsilane. This labeling experiment indicates that C-H bond cleavage is not the rate-determining step and that a rapid equilibrium prior to C-Si bond formation (i.e. the reductive elimination step) occurs in this catalytic reaction.

AB - The Ru3(CO)12-catalyzed reaction of aromatic compounds such as arylazoles, arylimines, and arylpyridines with triethylsilane (2) gave silylation products in good to excellent yields. Amide and ester groups could also be used as a directing group. In nearly all cases, C-Si bond formation took place at a position ortho to the directing groups. This coupling reaction is tolerant of both electron-donating and -withdrawing groups such as methoxy, fluoro, and trifluoromethyl groups. We expected that the use of 2-naphthyl-3-methylpyridine would not result in the formation of a coupling product, because the severe steric repulsion between the methyl group and the peri-hydrogen at the 8-position would strongly inhibit the attainment of a co-planar geometry. Interestingly, however, the reaction of 2-naphthyl-3-methylpyridine afforded the corresponding silylation product in quantitative yield. This observation indicates that the formation of metalacycle intermediate is not essential for the catalytic reaction to proceed. When a deuterium-labeling experiment using phenyloxazoline-d5 was carried out in the absence of olefin, partial H/D scrambling occurred between the ortho positions of the phenyloxazoline and the Si-H of triethylsilane. This labeling experiment indicates that C-H bond cleavage is not the rate-determining step and that a rapid equilibrium prior to C-Si bond formation (i.e. the reductive elimination step) occurs in this catalytic reaction.

KW - Aromatic C-H bonds

KW - C-H bond cleavage

KW - C-H/SiR coupling

KW - Ruthenium catalysts

KW - Triorganosilane

UR - http://www.scopus.com/inward/record.url?scp=0142057008&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0142057008&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(03)00448-0

DO - 10.1016/S0022-328X(03)00448-0

M3 - Article

AN - SCOPUS:0142057008

VL - 686

SP - 134

EP - 144

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -