Skip to main content
SpringerLink
Log in

Synthetic Aspects of the Metal-Mediated Cyclooligomerization of Phosphaalkynes

  • Chapter
Organic Synthesis via Organometallics (OSM 4)

Summary

Although the thermal cyclooligomerization of the phosphaalkyne 10 (≡ 4; R = tBu) proceeds non-selectively to furnish a mixture of 11, 12, and 13, the tetraphosphacubane 11 can be obtained in high yield from the reaction of the zirconium complex 15 with hexachloroethane. This reaction provides the starting point for numerous functionalization reactions at the phosphorus atoms of the pentacyclic system (→ 27–38, 40, and 42–46). In the presence of aluminium trihalides the phosphaalkynes 4 (R = tBu, 1-Ad) undergo spirocyclization with incorporation of the Lewis acid to furnish the 1,3-diphosphete betaines 50. Removal of the Lewis acid moiety by treatment with DMSO induces a rearrangement to the Dewar phosphabenzenes 52 and 53 which, in turn, can be trapped by homo-Diels-Alder reactions with the phosphaalkyne 10 (→ 54, 55). Isomerization reactions among the phosphaalkyne cyclotetramers 54, 55, 13, and 57 are discussed; they are in accord with the calculated heats of formation for the respective, unsubstituted molecules.

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 54.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 69.99
Price excludes VAT (USA)
  • Compact, lightweight 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. Organophosphorus Compounds; Part 64. For Part 63, see: H. Memmesheimer, M. Regitz in U. Brinker (Ed.): Advances in Carbene Chemistry, JAI Press, Greenwich, Connecticut 1992, in * press.

    Google Scholar 

  2. T. E. Gier, J. Am. Chem. Soc. 63 (1961) 1769.

    Article  Google Scholar 

  3. G. Becker, G. Gresser, W. Uhl, Z. Naturforsch. 36b(1981)16.

    CAS  Google Scholar 

  4. G. Becker, Z. Anorg. Allg. Chem. 430(1977)66.

    Article  CAS  Google Scholar 

  5. T. Allspach, M. Regitz, G. Becker, W. Becker, Synthesis 1986, 31.

    Google Scholar 

  6. W. Rösch, U. Vogelbacher, T. Allspach, M. Regitz, J. Organomet. Chem. 306(1986)39.

    Article  Google Scholar 

  7. M. Regitz, W. Rösch, T. Allspach, U. Annen, K. Blatter, J. Fink, M. Hermesdorf, H. Heydt, U. Vogelbacher, O. Wagner, Phosphorus Sulfur 30(1987)479.

    CAS  Google Scholar 

  8. W. Rösch, U. Hees, M. Regitz, Chem. Ber. 120(1987)1645.

    Article  Google Scholar 

  9. Review: M. Regitz, P. Binger, Angew. Chem. 100(1988)1541; Angew. Chem., Int. Ed. Engl. 27(1988)1484.

    Article  CAS  Google Scholar 

  10. Review: M. Regitz, Chem. Rev. 90(1990)191.

    Article  CAS  Google Scholar 

  11. Report: M. Regitz, Nachr. Chem. Tech. Lab. 37(1989)896.

    Article  CAS  Google Scholar 

  12. Report: M. Regitz in E. Blockz (Ed.): Heteroatom Chemistry, VCH Publisher, New York 1990, p. 295 ff.

    Google Scholar 

  13. Report: M. Regitz, Bull. Soc. Chim. Belg. 101(1992)359.

    Article  CAS  Google Scholar 

  14. Monograph: M. Regitz in M. Regitz, O. J. Scherer (Eds.): Multiple Bonds and Low Coordination in Phosphorus Chemistry, Thieme, Stuttgart 1990, p. 58 ff.

    Google Scholar 

  15. Cf. P. Binger, in Ref. [14], p. 90 ff.

    Google Scholar 

  16. Review: J. F. Nixon, Chem. Rev. 88(1988)1327.

    Article  CAS  Google Scholar 

  17. P. B. Hitchcock, U. J. Maah, J. F. Nixon, J. Chem. Soc., Chem. Commun. 1986, 737.

    Google Scholar 

  18. P. Binger, R. Milczarek, R. Mynott, M. Regitz, W. Rösch, Angew. Chem. 98(1986)645; Angew. Chem., Int. Ed. Engl. 25(1986)644; P. Binger, R. Milczarek, R. Mynott, C. Krüger, Y.-H. Tsay, E. Raabe, M. Regitz, Chem. Ber. 121 (1988) 637.

    Article  CAS  Google Scholar 

  19. P. Binger, B. Biedenbach, C. Krüger, M. Regitz, Angew. Chem. 99(1987)798; Angew. Chem., Int. Ed. Engl. 26(1987)764.

    Article  CAS  Google Scholar 

  20. A. R. Barron, A. H. Cowley, Angew. Chem. 99(1987)956; Angew. Chem., Int. Ed. Engl. 26(1987)907. All attempts to repeat this experiment to date have been unsuccessful (P. Binger, personal communication, Max-Planck-Institut für Kohlenforschung, Mülheim/Ruhr).

    Article  CAS  Google Scholar 

  21. P. Milczarek, W. Rüsseler, P. Binger, K. Jonas, K. Angermund, C. Krüger, M. Regitz, Angew. Chem. 99(1987)957; Angew. Chem., Int. Ed. Engl. 26(1987)908.

    Article  CAS  Google Scholar 

  22. M. Driess, D. Hu, H. Pritzkow, H. Schaufele, U. Zenneck, M. Regitz, W. Rösch, J. Organomet. Chem. 334(1987)C35.

    Article  CAS  Google Scholar 

  23. T. Wettling, J. Schneider, O. Wagner, C. G. Kreiter, M. Regitz, Angew. Chem. 101(1989)1035; Angew. Chem., Int. Ed. Engl. 28(1989)1013.

    Article  CAS  Google Scholar 

  24. T. Wettling, M. Regitz, unpublished results., University of Kaiserslautern 1990.

    Google Scholar 

  25. R. Gleiter, K.-H. Pfeifer, M. Baudler, G. Scholz, T. Wettling, M. Regitz, Chem. Ber. 123(1990)757.

    Article  CAS  Google Scholar 

  26. P. Binger, T. Wettling, R. Schneider, F. Zurmühlen, U. Bergsträßer, J. Hoffmann, G. Maas, M. Regitz, Angew. Chem. 103(1991)208; Angew. Chem., Int. Ed. Engl. 30(1991)207.

    Article  CAS  Google Scholar 

  27. T. Wettling, B. Geißler, R. Schneider, S. Barth, P. Binger, M. Regitz, Angew. Chem. 104(1992)761; Angew. Chem., Int. Ed. Engl. 31(1992)758.

    Article  CAS  Google Scholar 

  28. B. Geißler, M. Regitz, unpublished results, University of Kaiserslautern 1991.

    Google Scholar 

  29. P. Binger, B. Biedenbach, R. Schneider, M. Regitz, Synthesis 1989, 960.

    Google Scholar 

  30. H. Schumann, H. Benda, Angew. Chem. 80(1968)846; Angew. Chem., Int. Ed. Engl. 7(1968)813.

    Article  Google Scholar 

  31. M. Baudler, G. Scholz, K.-F. Tebbe, M. Feher, Angew. Chem. 101(1989)352; Angew. Chem. Int. Ed. Engl. 28(1989)339.

    Article  CAS  Google Scholar 

  32. A. H. Cowley, R. A. Jones, P. R. Harris, D. A. Attwood, L. Contreras, C. J. Burek, Angew. Chem. 103(1991)1164; Angew. Chem., Int. Ed. Engl. 30(1991)1143.

    Article  CAS  Google Scholar 

  33. M. Birkel, J. Schulz, U. Bergsträßer, M. Regitz, Angew. Chem. 104(1992)870; Angew. Chem., Int. Ed. Engl. 31(1992)879.

    Article  CAS  Google Scholar 

  34. Review: P. Stang, Angew. Chem. 104 (1992) 281; Angew. Chem., Int. Ed. Engl. 31(1992)274.

    Article  CAS  Google Scholar 

  35. K. K. Laali, M. Regitz, M. Birkel, P. Stang, C. Crittel, J. Org. Chem. 57(1993) in press.

    Google Scholar 

  36. M. Birkel, M. Regitz, unpublished results, University of Kaiserslautern 1992.

    Google Scholar 

  37. B. Breit, U. Bergsträßer, G. Maas, M. Regitz, Angew. Chem. 104(1992)1043; Angew. Chem., Int. Ed. Engl. 31(1992)1055.

    Article  CAS  Google Scholar 

  38. R. Appel, in Ref. [14], p. 160.

    Google Scholar 

  39. Compound 4 (R = tBu) was protonated at the same carbon atom by fluorosulfonic acid in liquid SO2: K. Laali, M. Regitz, unpublished results, Kent State University 1992.

    Google Scholar 

  40. P. B. J. Driesen, H. Hogeveen, J. Organomet. Chem. 156(1978)265.

    Article  Google Scholar 

  41. B. Breit, H. Heydt, M. Regitz, unpublished results, University of Kaiserslautern 1992.

    Google Scholar 

  42. E. P. O. Fuchs, M. Hermesdorf, W. Schnurr, W. Rösch, H. Heydt, M. Regitz, J. Organomet. Chem. 338 (1988) 329.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Fachbereich Chemie, Universität Kaiserslautern, Erwin-Schrödinger-Strasse, D-6750, Kaiserslautern, Federal Republic of Germany

    Manfred Regitz

Authors
  1. Manfred Regitz
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Institut für Organische Chemie, RWTH Aachen, Professor-Pirlet-Str. 1, D-W 5100, Aachen, Federal Republic of Germany

    Dieter Enders  & Hans-Joachim Gais  & 

  2. Institut für Technische Chemie und Petrochemie, RWTH Aachen, Professor-Pirlet-Str. 1, D-W 5100, Aachen, Federal Republic of Germany

    Wilhelm Keim

Rights and permissions

Reprints and permissions

Copyright information

© 1993 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH, Braunschweig/Wiesbaden

About this chapter

Cite this chapter

Regitz, M. (1993). Synthetic Aspects of the Metal-Mediated Cyclooligomerization of Phosphaalkynes. In: Enders, D., Gais, HJ., Keim, W. (eds) Organic Synthesis via Organometallics (OSM 4). Vieweg+Teubner Verlag. https://doi.org/10.1007/978-3-322-84062-2_8

Download citation

  • DOI: https://doi.org/10.1007/978-3-322-84062-2_8

  • Publisher Name: Vieweg+Teubner Verlag

  • Print ISBN: 978-3-528-06481-5

  • Online ISBN: 978-3-322-84062-2

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation