Synthesis of an electron-rich KITPHOS monophosphine, preparation of derived metal complexes and applications in catalysis

Academic Article


  • This protocol describes the synthesis of a representative example of the electron-rich biaryl-like KITPHOS class of monophosphine, 11- dicyclohexylphosphino-12-phenyl-9,10-dihydro-9,10-ethenoanthracene (H-KITPHOS). The bicyclic architecture of H-KITPHOS is constructed via [4+2] Diels-Alder cycloaddition between 1-(dicyclohexylphosphinoylethynyl)benzene and anthracene. H-KITPHOS monophosphine is prepared via an operationally straightforward three-step procedure and is isolated in an overall yield of ∼55%. The synthesis of palladium and gold precatalysts of H-KITPHOS are also described; the yields of analytically pure complexes are high (75-85% and 85-90%, respectively). The palladium complex of H-KITPHOS forms a highly active catalyst for C-C and C-N cross-coupling of a range of aryl and heteroaryl chlorides and bromides, and the electrophilic Lewis acid gold complex efficiently catalyzes a host of cycloisomerizations. The total time required for the synthesis of H-KITPHOS is 95 h; the preparation of corresponding palladium and gold precatalysts requires an additional 7-8 h, and, if necessary, crystallizations will require a further 48 h. © 2012 Nature America, Inc. All rights reserved.
  • Authors

    Published In

  • Nature Protocols  Journal
  • Digital Object Identifier (doi)

    Author List

  • Doherty S; Smyth CH; Knight JG; Hashmi SAK
  • Start Page

  • 1870
  • End Page

  • 1883
  • Volume

  • 7
  • Issue

  • 10