Equilibrium shift in the rhodium-catalyzed acyl transfer reactions

Mieko Arisawa, Yui Igarashi, Haruki Kobayashi, Toru Yamada, Kentaro Bando, Takuya Ichikawa, Masahiko Yamaguchi

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Rhodium/phosphine complexes catalyze equilibrium acyl transfer reactions between acid fluorides, aryl esters, acylphosphine sulfides, and thioesters. The use of appropriate co-substrates to accept heteroatom groups shifted the equilibrium to desired products. Acylphosphine sulfides and aryl esters were converted to acid fluorides using benzoylpentafluorobenzene as the fluoride donor, and the fluorination reaction of thioesters employed (4-tolylthio) pentafluorobenzene. Acid fluorides were converted into acylphosphine sulfides and thioesters using diphosphine disulfides and disulfides/triphenylphosphine, respectively. Aryl esters were obtained from acid fluorides and phenols in the presence of triphenylsilane. Aryl esters, acylphosphine sulfides, and thioesters were also interconverted in the presence of rhodium complexes. These rhodium-catalyzed acyl transfer reactions proceeded under neutral conditions without using acid or base. The involvement of acyl rhodium intermediates in these reactions was suggested by the carbothiolation reaction of thioesters and alkynes.

Original languageEnglish
Pages (from-to)7846-7859
Number of pages14
JournalTetrahedron
Volume67
Issue number40
DOIs
Publication statusPublished - 2011 Oct 7

Keywords

  • Acyl transfer
  • Co-product
  • Co-substrate
  • Equilibrium
  • Rhodium catalyst

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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  • Cite this

    Arisawa, M., Igarashi, Y., Kobayashi, H., Yamada, T., Bando, K., Ichikawa, T., & Yamaguchi, M. (2011). Equilibrium shift in the rhodium-catalyzed acyl transfer reactions. Tetrahedron, 67(40), 7846-7859. https://doi.org/10.1016/j.tet.2011.07.031