Systematic study on the catalytic synthesis of unsaturated 2-ketocarboxamides

Palladium-catalyzed double carbonylation of 1-iodocyclohexene

Rui M B Carrilho, Mariette M. Pereira, Attila Takács, L. Kollár

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

1-Iodocyclohexene, a benchmark substrate, has been double carbonylated in the presence of palladium-phosphite precatalysts. Triarylphosphites with OR substituents, able to act both as P-monodentate and hemilabile P,O-heterobidentate ligands were used in this reaction. Systematic investigations have revealed that the chemoselectivity towards cyclohexenylglyoxylamides, i.e., the products obtained in aminocarbonylation by the insertion of two carbon monoxide, is strongly influenced by the amine nucleophile, temperature and carbon monoxide pressure. The highest yields of 2-ketocarboxamides were obtained at low temperature (30 °C) and high carbon monoxide pressure (110 bar). However, the structure of the phosphite ligand has practically no effect either on catalytic activity or chemoselectivity. This fact refers to the P-monodentate coordination of the ligands in catalytic intermediates or that palladium nanoparticles are the catalytically active species.

Original languageEnglish
Pages (from-to)204-207
Number of pages4
JournalTetrahedron
Volume68
Issue number1
DOIs
Publication statusPublished - Jan 7 2012

Fingerprint

Carbonylation
Palladium
Carbon Monoxide
Phosphites
Ligands
Pressure
Benchmarking
Nucleophiles
Temperature
Nanoparticles
Amines
Catalyst activity
Substrates

Keywords

  • Amino acids
  • Carbon monoxide
  • Carbonylation
  • Homogeneous catalysis
  • Palladium

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Systematic study on the catalytic synthesis of unsaturated 2-ketocarboxamides : Palladium-catalyzed double carbonylation of 1-iodocyclohexene. / Carrilho, Rui M B; Pereira, Mariette M.; Takács, Attila; Kollár, L.

In: Tetrahedron, Vol. 68, No. 1, 07.01.2012, p. 204-207.

Research output: Contribution to journalArticle

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