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

Nature Protocols volume 7, pages 1870–1883 (2012)Cite this article

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Abstract

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.

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Figure 1
Figure 2
Figure 3: KITPHOS monophosphine 9 and complexes described here.
Figure 4: Synthesis of electron-rich biaryl-like KITPHOS monophosphines.
Figure 5: Synthesis of the palladium and gold precatalysts.
Figure 6

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Acknowledgements

We are extremely grateful to the UK Engineering and Physical Science Research Council (EPSRC) for funding (C.H.S.) and J. Matthey for generous loans of platinum group metal salts.

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  1. School of Chemistry, Newcastle University, Newcastle upon Tyne, UK

    Simon Doherty, Catherine H Smyth & Julian G Knight

  2. Organisch-Chemisches Institut, Universität Heidelberg, Heidelberg, Germany

    Stephen A K Hashmi

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Contributions

S.D. supervised the project and wrote the manuscript, C.H.S. conducted all the synthesis, as well as the palladium-based catalysis reported in the original papers, tested the protocols and edited the manuscript. J.G.K. edited the manuscript and S.A.K.H. conducted the gold catalysis and edited the manuscript.

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Correspondence to Simon Doherty.

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Supplementary Figure 1

Photograph showing the Asynt DrySyn® multi-position heating block and Wheaton V-20 reaction vials used for the Diels-Alder cycloaddition between anthracene and (dicyclohexylphosphinoylethynyl)benzene. (PDF 14519 kb)

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Doherty, S., Smyth, C., Knight, J. et al. Synthesis of an electron-rich KITPHOS monophosphine, preparation of derived metal complexes and applications in catalysis. Nat Protoc 7, 1870–1883 (2012). https://doi.org/10.1038/nprot.2012.107

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