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Preparation of dicationic palladium catalysts for asymmetric catalytic reactions

Nature Protocols volume 7, pages 1765–1773 (2012)Cite this article

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Abstract

The synthesis of Pd(OTf)2·2H2O is described. This was used to generate two different types of chiral dicationic palladium complexes for highly enantioselective addition of aromatic amines to α, β-unsaturated conjugate alkenes ([(R-BINAP)Pd(OH2)2][OTf]2 and [(R-BINAP)Pd(μ-OH)]2[OTf]2). The resulting optically active N-arylated β-amino acid derivatives are valuable synthetic intermediates for the synthesis of biologically active molecules and peptidomimetics. The reaction of (2E)-but-2-enoylcarbamate and aniline is shown as an example of the use of these catalysts for enantioselective aza-Michael addition. For the preparation of palladium(II) triflate, the time scale is 20 h 50 min, plus 5 h 15 min for the monomeric complex and plus 6 h 45 min for the dimeric complex.

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Figure 1: Monomeric and dimeric forms of dicationic diphosphine palladium(II) complexes.
Figure 2
Figure 3: Enantioselective addition of an aromatic amine to an N-alkenoyl carbamate.
Figure 4
Figure 5: Equipment setup for the preparation of Pd(OTf)2·2H2O (Steps 1–4).
Figure 6: Photographs showing the progress of the reaction.
Figure 7: Photographs showing the progress of the reaction.
Figure 8
Figure 9
Figure 10: Appearance of palladium compounds.
Figure 11: Chiral HPLC chromatograms of (3-phenylaminobutyryl)carbamic acid methyl ester.
Figure 12

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Acknowledgements

A.E.S. is supported by a Marie Curie Intra-European Fellowship within the 7th European Community Framework Programme (Project 252247).

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Authors and Affiliations

  1. Department of Chemistry, Imperial College London, South Kensington, London, UK

    Andrey E Sheshenev, Alexander M R Smith & King Kuok (Mimi) Hii

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  1. Andrey E Sheshenev
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Contributions

A.M.R.S. refined the original procedures for catalyst preparation; A.E.S. carried out the experimental procedure and aza-Michael reactions; and K.K.H. assembled the manuscript.

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Correspondence to King Kuok (Mimi) Hii.

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Sheshenev, A., Smith, A. & Kuok (Mimi) Hii, K. Preparation of dicationic palladium catalysts for asymmetric catalytic reactions. Nat Protoc 7, 1765–1773 (2012). https://doi.org/10.1038/nprot.2012.095

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