Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins

Gabriela A. Grasa, Rohit Singh, Edwin D. Stevens, Steven P. Nolan

Research output: Contribution to journalArticlepeer-review

122 Scopus citations

Abstract

Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs2CO3 as base was tested using various substrates. The Pd(OAc)2/ DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)2 (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of nBu4NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)2 and Pd(acac)2 /DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.

Original languageEnglish (US)
Pages (from-to)269-279
Number of pages11
JournalJournal of Organometallic Chemistry
Volume687
Issue number2
DOIs
StatePublished - Dec 7 2003
Externally publishedYes

Keywords

  • Diazabutadienes
  • Heck coupling
  • Palladium

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