Skip to main content
SpringerLink
Log in

Phosphine-Free EWG-Activated Ruthenium Olefin Metathesis Catalysts

  • Conference paper
Metathesis Chemistry

Part of the book series: NATO Science Series ((NAII,volume 243))

Hoveyda–Grubbs catalyst has been successfully fine-tuned by us in order to increase its activity and applicability by the introduction of electron-withdrawing groups (EWGs) to diminish donor properties of the oxygen atom. As a result, the stable and easily accessible nitro-substituted Hoveyda–Grubbs catalyst has found a number of successful applications in various research and industrial laboratories. Some other EWG-activated Hoveyda-type catalysts are commercially available. The results described herewith demonstrate that the activity of ruthenium (Ru) metathesis catalysts can be enhanced by introduction of EWGs without detriment to catalysts stability. Equally noteworthy is the observation that different Ru catalysts turned out to be optimal for different applications. This shows that no single catalyst outperforms all others in all possible applications.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Astruc, D., New, J., Chem. 2005, 29:42.

    CAS  Google Scholar 

  2. Grubbs, R.H. (ed.), Handbook of Metathesis, Vols. 1-3 Wiley-VCH, Weinheim, 2003.

    Google Scholar 

  3. General reviews, see [1-2] and: (a) Grubbs, R.H., Chang, S., Tetrahedron 1998, 54;4413; (b) Schrock, R.R., Top. Organomet. Chem. 1998, 1:31; (c) Fürstner, A., Angew. Chem. Int. Edit. 2000, 39:3012; (d) Trnka, T.M., Grubbs, R.H., Acc. Chem. Res. 2001, 34:18; (e) For selected key papers on achiral and chiral molybdenum catalysts, see: Hoveyda, A.H., Schrock, R.R., Chem. Eur. J. 2001, 7:945; (f) Schrock, R.R., Hoveyda, A.H., Angew. Chem. Int. Edit. 2003, 38:4555; (g) Schrock, R.R., Pure Appl. Chem. 1994, 66:1447; (h) Murdzek, J.S., Schrock, R.R., Organometallics 1987, 6:1373.

    Google Scholar 

  4. The importance of “the development of the metathesis method in organic synthesis” has been recently recognized by awarding the Nobel Prize in Chemistry for 2005 jointly to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock, see: http://http://nobelprize.org/chemistry/laureates/2005/chemadv05.pdf for more details.

  5. (a) Kingsbury, J.S., Harrity, J.P.A., Bonitatebus, P.J., Hoveyda, A.H.J., Am. Chem. Soc. 1999, 121:791; (b) Garber, S.B., Kingsbury, J.S., Gray, B.L., Hoveyda, A.H.J., Am. Chem. Soc. 2000, 122:8168; (c) Gessler, S., Randl, S., Blechert, S., Tetrahedron Lett. 2000, 41:9973.

    Google Scholar 

  6. (a) For a short review, see: Hoveyda, A.H., Gillingham, D.G., Van Veldhuizen, J. J., Kataoka, O., Garber, S.B., Kingsbury, J.S., Harrity, J.P.A., Org. Biomol. Chem. 2004, 2:1.

    Google Scholar 

  7. (a) Wakamatsu, H., Blechert, S., Angew. Chem. Int. Edit. 2002, 41:794; (b) Wakamatsu, H., Blechert, S., Angew. Chem. Int. Edit. 2002, 41:2403; (c) For an improved synthesis of 5 and reactivity studies, see: Dunne, A.M., Mix, S., Blechert, S., Tetrahedron. Lett. 2003, 44:2733.

    Google Scholar 

  8. Grela, K., Tryznowski, M., Bieniek, M., Tetrahedron Lett. 2002, 43:9055.

    Article  CAS  Google Scholar 

  9. Grela, K., Harutyunyan, S., Michrowska, A., Angew. Chem. Int. Edit., 2002, 41:4038.

    Article  CAS  Google Scholar 

  10. (a) Michrowska, A., Bujok, R., Harutyunyan, S., Sashuk, V., Dolgonos, G., Grela, K.J., Am. Chem. Soc.2004,126:9318; (b) Harutyunyan, S., Michrowska, A., Grela, K., in: Roberts, S. (ed.), Catalysts for Fine Chemical Synthesis, Vol. 3, Wiley Interscience, Hoboken, NJ, 2004, Chap. 9.1, pp. 169; (c) Grela, K., US Patent 6,867,303.

    Google Scholar 

  11. Bieniek, M., Bujok, R., Stępowska, H., Jacobi, A., Hagenkötter, R., Arlt, D., Jarzembska, K., Woźniak, K., Grela, K., J. Organomet. Chem. (in press).

    Google Scholar 

  12. Boehringer Ingelheim International GmbH, EP 03 027828.7, 2003.

    Google Scholar 

  13. Bujok, R., Grela, K., unpublished data.

    Google Scholar 

  14. Rix, D., Clavier, H., Gulajski, L., Grela, K., Mauduit, M., J. Organomet. Chem. 2006 (in press).

    Google Scholar 

  15. Dunne, A.M., Mix, S., Blechert, S., Tetrahedron Lett. 2003, 44:2733.

    Article  CAS  Google Scholar 

  16. (a) Gułajski, Ł., Michrowska, A., Bujok, R., Grela, K., J. Mol. Catal. A: Chem.2005,254:118; (b) Michrowska, A., Mennecke, K., Kunz, U., Kirschning, A., Grela, K., J. Am. Chem. Soc. 2006 (in press).

    Google Scholar 

  17. Michrowska, A., Gułajski, Ł., Kaczmarska, Z., Mennecke, K., Kirschning, A., Grela, K., Green Chem. 2006, 8:685.

    Article  CAS  Google Scholar 

  18. EWG-activated Hoveyda-type catalyst is available commercially from Strem Chemicals, Inc. and from Zannan Pharma.

    Google Scholar 

  19. For reviews on catalytic cross-metathesis, see: (a) Blechert, S., Connon, S.J., Angew. Chem. Int. Edit. 2003, 42:1900; (b) Vernall, A.J., Abell, A.D., Aldrichimica Acta 2003, 36:93; (c) Blackwell, H.E., O’Leary, D.J., Chatterjee, A.K., Washenfelder, R.A., Bussmann, D.A., Grubbs, R.H., J. Am. Chem. Soc. 2000, 122:58; (d) For a short review on applications to commercial products, see: Pederson, R.L., Fellows, I.M., Ung, T.A., Ishihara, H., Hajela, S.P., Adv. Synth. Catal. 2002, 344:728; (e) For a general model for selectivity in olefin CM, see Chatterjee, A.K., Choi, T.-L., Sanders, D.P., Grubbs, R.H., J. Am. Chem. Soc. 2003, 125:11360. 124K. Grela et al.

    Google Scholar 

  20. Previously, a failure in the CM reaction of vinyl sulfones was reported, see: (a) Chatterjee, A.K., Morgan, J.P., Scholl, M., Grubbs, R.H., J. Am. Chem. Soc. 2000, 122:3783; (b) Randl, S., Blechert, S., unpublished data; see Ref. 47.

    Google Scholar 

  21. (a) Evans, P., Leffray, M., Tetrahedron 2003, 59:7973; (b) Au, C.W.G., Pyne S.G., J. Org. Chem. 2006, 71:7097.

    Google Scholar 

  22. Teyssot, M.-L., Fayolle, M., Philouze, C., Dupuy, C., Eur. J. Org. Chem. 2003, 54, and references cited therein.

    Google Scholar 

  23. Bieniek, M., Kołoda, D., Grela, K., Org. Lett. (in press).

    Google Scholar 

  24. Pietrusiewicz, K.M., Zablocka, M., Chem. Rev. 1994, 94:1375.

    Article  CAS  Google Scholar 

  25. Demchuk, O.M., Pietrusiewicz, K.M., Michrowska, A., Grela, K., Org. Lett. 2003, 5:3217.

    Article  CAS  Google Scholar 

  26. (a) Choi, T.L., Lee, C.W., Chatterjee, A.K., Grubbs, R.H., J. Am. Chem. Soc. 2001, 123:10417; (b) Yao, Q., Motta, A.R., Tetrahedron Lett. 2004, 45:2447.

    Google Scholar 

  27. Vinokurov, N., Michrowska, A., Szmigielska, A., Drzazga, Z., Wójciuk, G., Demchuk, O.M., Grela, K., Pietrusiewicz, K.M., Butenschön, H. Adv. Synth. Catal. 2006, 348:931.

    Article  CAS  Google Scholar 

  28. Mikus, A., Sashuk, V., Kędziorek, M., Samojłowicz, C., Ostrowski, S., Grela, K., Synlett 2005, 1142.

    Google Scholar 

  29. Szadkowska, A., Grela, K., unpublished data.

    Google Scholar 

  30. (a) Bujok, R., Bieniek, M., Masnyk, M., Michrowska, A., Sarosiek, A., Stępowska, H., Arlt, D., Grela, K., J. Org. Chem. 2004, 69:6894; (b) Bieniek, M., Michrowska, A., Gułajski, Ł., Grela, K., Organometallics 2006 (accepted).

    Google Scholar 

  31. Honda, T., Namiki, H., Watanabe, M., Mizutani, H., Tetrahedron Lett. 2004, 45:5211.

    Article  CAS  Google Scholar 

  32. Honda, T., Namiki, H., Kaneda, K., Mizutani, H., Org. Lett. 2004, 6:87.

    Article  CAS  Google Scholar 

  33. (a) Ostrowski, S., Mikus, A., Heterocycles 2005, 65:2339; (b) Ostrowski, S., Mikus, A., Mol. Diversity 2003, 6:315.

    Google Scholar 

  34. PTC Patent Application WO2004/089974 A1, Boehringer Ingelheim International, 2004.

    Google Scholar 

  35. Lamarre, D., Anderson, P.C., Bailey, M.D., Beaulieu, P., Bolger, G., Bonneau, P., Bos, M., Cameron, D.R., Cartier, M., Cordingley, M.G., Faucher, A.M., Goudreau, N., Kawai, S.H., Kukolj, G., Lagace, L., LaPlante, S.R., Narjes, H., Poupart, M.A., Rancourt, J., Sentjens, R.E., St George, R., Simoneau, B., Steinmann, G., Thibeault, D., Tsantrizos, Y.S., Weldon, S.M, Yong C.L., Llinas-Brunet, M., Nature 2003, 426:186.

    Article  CAS  Google Scholar 

  36. Faucher, A.M., Bailey, M.D., Beaulieu, P.L., Brochu, C., Duceppe, J.S., Ferland, J.M., Ghiro, E., Gorys, V., Halmos, T., Kawai, S.H., Poirier, M., Simoneau, B., Tsantrizos, Y.S., Llinas-Brunet, M., Org. Lett. 2004, 6:2901.

    Google Scholar 

  37. Nicola, T., Brenner, M., Donsbach, K., Kreye, P., Org. Proc. Res. Devel. 2005, 9:513.

    Article  CAS  Google Scholar 

  38. Bieniek, M., Bujok, R., Stępowska, H., Jacobi, A., Hagenkötter, R., Arlt, D., Jarzembska, K., Woźniak, K., Grela, K., J. Organomet. Chem. 2006 (in press).

    Google Scholar 

  39. Stellfeld, T., Bhatt, U., Kalesse, M., Org. Lett. 2004, 6:3889.

    Article  CAS  Google Scholar 

  40. Albert, B.J., Sivaramakrishnan, A., Naka, T., Koide, K., J. Am. Chem. Soc. 2006, 128:2792.

    Article  CAS  Google Scholar 

  41. Goldup, S.M., Pilkington, C.J., White, A.J.P., Burton, A., Barrett, A.G.M., J. Org. Chem. 2006, 71:6185.

    Article  CAS  Google Scholar 

  42. Leitner, W. in Forschungsbericht2002-2004, Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr,2005, p.60; http://www.mpimuelheim.mpg.de/kofo/bericht2005/bereiche/alles.pdf

Download references

Author information

Authors and Affiliations

  1. Polish Academy of Sciences, Institute of Organic Chemistry, Kasprzaka 44/52, 01-224, Warsaw, Poland

    Karol Grela, Anna Szadkowska, Anna Michrowska, Michal Bieniek & Volodymyr Sashuk

Authors
  1. Karol Grela
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anna Szadkowska
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Anna Michrowska
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Michal Bieniek
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Volodymyr Sashuk
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Hacettepe University, 06800, Beytepe, Ankara, Turkey

    Yavuz Imamoglu

  2. Romanian Academy, Bucharest, Romania

    Valerian Dragutan

  3. Hacettepe University, 06800, Beytepe, Ankara, Turkey

    Solmaz Karabulut

Rights and permissions

Reprints and permissions

Copyright information

© 2007 Springer

About this paper

Cite this paper

Grela, K., Szadkowska, A., Michrowska, A., Bieniek, M., Sashuk, V. (2007). Phosphine-Free EWG-Activated Ruthenium Olefin Metathesis Catalysts. In: Imamoglu, Y., Dragutan, V., Karabulut, S. (eds) Metathesis Chemistry. NATO Science Series, vol 243. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6091-5_6

Download citation

Publish with us

Policies and ethics

Search

Navigation