Dichloro-bis(aminophosphine) complexes of palladium: highly convenient, reliable and extremely active suzuki-miyaura catalysts with excellent functional group tolerance

Chemistry. 2010 Apr 6;16(13):4075-81. doi: 10.1002/chem.200903309.

Abstract

Dichloro-bis(aminophosphine) complexes are stable depot forms of palladium nanoparticles and have proved to be excellent Suzuki-Miyaura catalysts. Simple modifications of the ligand (and/or the addition of water to the reaction mixture) have allowed their formation to be controlled. Dichlorobis[1-(dicyclohexylphosphanyl)piperidine]palladium (3), the most active catalyst of the investigated systems, is a highly convenient, reliable, and extremely active Suzuki catalyst with excellent functional group tolerance that enables the quantitative coupling of a wide variety of activated, nonactivated, and deactivated and/or sterically hindered functionalized and heterocyclic aryl and benzyl bromides with only a slight excess (1.1-1.2 equiv) of arylboronic acid at 80 degrees C in the presence of 0.2 mol % of the catalyst in technical grade toluene in flasks open to the air. Conversions of >95 % were generally achieved within only a few minutes. The reaction protocol presented herein is universally applicable. Side-products have only rarely been detected. The catalytic activities of the aminophosphine-based systems were found to be dramatically improved compared with their phosphine analogue as a result of significantly faster palladium nanoparticle formation. The decomposition products of the catalysts are dicyclohexylphosphinate, cyclohexylphosphonate, and phosphate, which can easily be separated from the coupling products, a great advantage when compared with non-water-soluble phosphine-based systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cross-Linking Reagents / chemistry
  • Crystallography, X-Ray
  • Ligands
  • Models, Molecular
  • Nanoparticles / chemistry*
  • Organometallic Compounds / chemistry*
  • Palladium / chemistry*
  • Phosphines / chemistry*
  • Stereoisomerism

Substances

  • Cross-Linking Reagents
  • Ligands
  • Organometallic Compounds
  • Phosphines
  • dichlorobis(1-(dicyclohexylphosphanyl)piperidine)palladium
  • Palladium