Ruthenium- and rhodium-catalyzed direct carbonylation of the ortho C-H bond in the benzene ring of N-arylpyrazoles

Taku Asaumi, Takuya Matsuo, Takahide Fukuyama, Yutaka Ie, Fumitoshi Kakiuchi, Naoto Chatani

Research output: Contribution to journalArticle

66 Citations (Scopus)

Abstract

The direct carbonylation of C-H bonds in the benzene ring of N-phenylpyrazoles via catalysis by ruthenium or rhodium complexes is described. The reaction of N-phenylpyrazoles with carbon monoxide and ethylene in the presence of Ru3(CO)12 or Rh4(CO)12 resulted in the site-selective carbonylation of the ortho C-H bonds in the benzene ring to give the corresponding ethyl ketones. A variety of functional groups on the benzene ring can be tolerated. N-Phenylpyrazoles have higher reactivities than would be expected, based on the pKa values of the conjugate acid of pyrazole. The choice of solvent for this reaction is significant, and N, N-dimethylacetamide (DMA) gives the best result.

Original languageEnglish
Pages (from-to)4433-4440
Number of pages8
JournalJournal of Organic Chemistry
Volume69
Issue number13
DOIs
Publication statusPublished - 2004 Jun 25
Externally publishedYes

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Carbonylation
Rhodium
Ruthenium
Carbon Monoxide
Benzene
Ketones
Functional groups
Catalysis
Acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Ruthenium- and rhodium-catalyzed direct carbonylation of the ortho C-H bond in the benzene ring of N-arylpyrazoles. / Asaumi, Taku; Matsuo, Takuya; Fukuyama, Takahide; Ie, Yutaka; Kakiuchi, Fumitoshi; Chatani, Naoto.

In: Journal of Organic Chemistry, Vol. 69, No. 13, 25.06.2004, p. 4433-4440.

Research output: Contribution to journalArticle

Asaumi, Taku ; Matsuo, Takuya ; Fukuyama, Takahide ; Ie, Yutaka ; Kakiuchi, Fumitoshi ; Chatani, Naoto. / Ruthenium- and rhodium-catalyzed direct carbonylation of the ortho C-H bond in the benzene ring of N-arylpyrazoles. In: Journal of Organic Chemistry. 2004 ; Vol. 69, No. 13. pp. 4433-4440.
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