Substituent effects in aminocarbonylation of para-substituted iodobenzenes

Diána Marosvölgyi-Haskó, Tamás Kégl, L. Kollár

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Iodobenzene derivatives possessing various substituents (amino, hydroxy, tert-butyl, methyl, isopropyl, phenyl, fluoro, chloro, methoxycarbonyl, acetyl, trifluoromethyl, nitro) in the para position were aminocarbonylated using tert-butylamine and n-butylamine as N-nucleophiles. A palladium(0) catalyst formed in situ from palladium(II) acetate and triphenylphosphine was used. Carboxamide and ketocarboxamide type compounds were formed via single and double carbon monoxide insertion, respectively. While 4-substituents with negative Hammett constants (σp) decrease reactivity of the substrates, the iodoaromatics possessing electron-withdrawing group (characterized by positive Hammett constants (σp)) in the 4-position have shown high reactivity. Highly active catalysts were obtained in the presence of xantphos accompanied by the chemoselective formation of the corresponding carboxamides. The difference in reactivity of iodoarene and bromoarene functionalities enabled the synthesis of bromo-substituted compounds suitable for further functionalization.

Original languageEnglish
Pages (from-to)7509-7516
Number of pages8
JournalTetrahedron
Volume72
Issue number47
DOIs
Publication statusPublished - Nov 24 2016

Fingerprint

Iodobenzenes
Palladium
Carbon Monoxide
Electrons
Nucleophiles
Catalysts
Derivatives
Substrates
iodobenzene
tert-butylamine
xantphos
n-butylamine
triphenylphosphine
palladium(II) acetate

Keywords

  • Carbon monoxide
  • Carbonylation
  • Carboxamide
  • Hammett constant
  • Iodoarene
  • Palladium

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Substituent effects in aminocarbonylation of para-substituted iodobenzenes. / Marosvölgyi-Haskó, Diána; Kégl, Tamás; Kollár, L.

In: Tetrahedron, Vol. 72, No. 47, 24.11.2016, p. 7509-7516.

Research output: Contribution to journalArticle

Marosvölgyi-Haskó, Diána ; Kégl, Tamás ; Kollár, L. / Substituent effects in aminocarbonylation of para-substituted iodobenzenes. In: Tetrahedron. 2016 ; Vol. 72, No. 47. pp. 7509-7516.
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