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 journalArticlepeer-review

112 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

Keywords

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

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'The ruthenium-catalyzed silylation of aromatic C-H bonds with triethylsilane'. Together they form a unique fingerprint.

Cite this