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Synthesis Optimization and Catalytic Activity Screening of Industrially Relevant Ruthenium-Based Metathesis Catalysts

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Abstract

Olefin metathesis is a powerful catalytic reaction that has a huge potential in the pharmaceutical, polymer and specialty chemicals industries. Cost-effective industrial applications require large-scale availability of catalyst precursors which combine high activity, high selectivity and long life-time. Among the known numerous families of olefin metathesis catalysts, the Umicore M7-catalyst family represents a novel class of Hoveyda-type complexes showing excellent chemical stabilities and modular activity profiles. Relevant aspects related to their industrial synthesis as well as their catalytic performance in valuable olefin metathesis transformations are overviewed here.

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Notes

  1. Selected comprehensive reviews on olefin metathesis [1–3].

  2. For industrial perspectives, see [4, 5].

  3. For a recent review on olefin metathesis in total synthesis, see [6].

  4. For a special review dealing with the development of NHC-Ru based complexes, see [7].

  5. For modifications of the reactive carbene, see for example [8–14].

  6. For pre-catalysts efficient at low loading, see for example [15–20].

  7. For pre-catalysts efficient at low loading, see for example [16, 18, 20].

  8. For enantioselective OM, see for instance [21–25].

  9. Selected examples for Z-selective OM, see [26–31].

  10. For modifications of the reactive carbene, see for example [8–14].

  11. For a recent review dealing with Ru-contamination, see [31].

  12. Reference [14].

  13. References 32–35].

  14. For a reviews dealing with the valorization of renewable resources via OM, see [36, 37]; For valuable synthetic applications with M7 complexes, see [39 40].

  15. For valuable synthetic applications with M7 complexes, see [38, 40].

  16. References [42, 43]

  17. Reference [42].

  18. Reference [44].

  19. References [32–34]; For valuable synthetic applications with M7 complexes, see [40].

  20. Reference [35].

  21. Reference [40].

  22. For valuable synthetic applications with M7 complexes, see [38, 40].

  23. Herbarumin I displayed significant phytotoxic effects, see [45]; For a pionner enantioselective total synthesis of Herbarumin I involving a RCM macrocyclisation step, see [46, 47].

  24. Reference [48].

  25. δ-decalactone is used in foods and beverages for its peach-like odour and cream flavour, see [49–51].

  26. Exaltolide belongs to the musk-ketone family and is used as a base note in perfumery, see [52]; For previous synthesis of Exaltolide using a RCM macrocyclisation step, see [53, 54].

  27. For valuable synthetic applications with M7 complexes, see [55].

  28. For valuable synthetic applications with M7 complexes, see [38].

  29. For valuable synthetic applications with M7 complexes, see [40].

  30. Reference [34]; For valuable synthetic applications with M7 complexes, see [41].

  31. Reference [34].

  32. Reference [35]; For valuable synthetic applications with M7 complexes, see [39].

  33. For valuable synthetic applications with M7 complexes, see [39].

  34. For valuable synthetic applications with M7 complexes, see [40].

  35. See for instance : [55].

  36. Aplysamine 6 displayed good activity as an inhibitor of isoprenylcysteine carboxyl methyltransferase, see [56–58].

  37. See footnote 34.

  38. Reference [34]

  39. For a recent review dealing with Ru-contamination, see [31].

  40. For a recent review dealing with Ru-contamination, see [31].

  41. Reference [34].

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Acknowledgments

Funding for this project was partially provided by the Agence Nationale de la Recherche (Project CFLOW-OMANR-2012-CDII-0002, Grant to S.B.) and by Rennes-Métropole. M.M. and F.C. thank the Region Bretagne for its financial support (Fonds de Maturation Feder N° 09005612).

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Authors and Affiliations

  1. Precious Metals Chemistry, Umicore AG & Co. KG, Rodenbacher Chaussee 4, 63457, Hanau, Germany

    Angelino Doppiu

  2. OMEGA CAT SYSTEM Sarl, Ecole Nationale Supérieure de Chimie de Rennes, 11 Avenue de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France

    Frederic Caijo & Fabien Tripoteau

  3. CNRS, UMR 6226, Ecole Nationale Supérieure de Chimie de Rennes, 11 Avenue de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France

    Savinien Bompard, Christophe Crévisy & Marc Mauduit

Authors
  1. Angelino Doppiu
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  2. Frederic Caijo
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  3. Fabien Tripoteau
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  4. Savinien Bompard
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  5. Christophe Crévisy
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  6. Marc Mauduit
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Correspondence to Angelino Doppiu.

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Doppiu, A., Caijo, F., Tripoteau, F. et al. Synthesis Optimization and Catalytic Activity Screening of Industrially Relevant Ruthenium-Based Metathesis Catalysts. Top Catal 57, 1351–1358 (2014). https://doi.org/10.1007/s11244-014-0302-8

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