Skip to main content
SpringerLink
Log in

Total Synthesis of Nitrogen-Containing Natural Products via Nitroso Diels-Alder Reaction

  • Conference paper
Natural Products Chemistry III

  • 214 Accesses

Abstract

Hetero Diels-Alder reaction in which the C-nitroso moiety (R-N=0) functions as a heterodienophile provides cyclic derivatives of hydroxylamine namely 3,6-dihydro-l,2-oxazines 1 (ref. 1). A synthetically important feature of the products is introduction of nitrogen and oxygen functionality at the same time with a high degree of regiochemical and stereochemical control. Subsequent reduction of these cycloadducts can easily be achieved by using a wide variety of reducing agents, such as zinc in acetic acid, sodium or aluminum amalgam in ethanol, or hydrogen over catalysts, and normally result in cleavage of the N-O bond leading to the formation of 4-amino alcohols.

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 129.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
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. For reviews of heterodinophile cycloadditions see: S. M. Weinreb and J. I. Levin, Heterocycles, 12, 949 (1979).

    Article  CAS  Google Scholar 

  2. S. M. Weinreb and R. S. Staib, Tetrahedron, 38 3127 (1982).

    Article  Google Scholar 

  3. S. M. Weinreb, Acc. Chem. Res., 18, 16 (1985).

    Article  CAS  Google Scholar 

  4. ref. 2c.

    Google Scholar 

  5. H. L. Holmes in “The Alkaloids,” R. H. F. Manske, Ed., Academic Press, New York, 1950, Vol. I, Chapter 6.

    Google Scholar 

  6. R. Robinson, J. Chem. Soc., 111, 762 (1917).

    CAS  Google Scholar 

  7. J. J. Tufariello and E. J. Trybulski, J. Chem. Soc., Chem. Commun., 720 (1973).

    Google Scholar 

  8. J. J. Tufariello, G. B. Mullen, J. J. Tegeler, E. J. Trybulski, S. C. Wang, and Sk. Asrof Ali, J. Am. Chem. Soc., 101, 2435 (1979).

    CAS  Google Scholar 

  9. R. Noyori, Y. Baba, and Y. Hayakawa, J. Am. Chem. Soc., 96, 3336 (1974).

    Article  CAS  Google Scholar 

  10. Y. Hayakawa, Y. Baba, Y. Makino, and R. Noyori, Ibid., 100, 1786 (1978).

    CAS  Google Scholar 

  11. For recent entries into natural products utilizing nitroso Diels-Alder reactions, see: N. J. Leonard and A. J. Playtis, J. Chem. Soc., Chem. Commun., 133 (1972).

    Google Scholar 

  12. G. E. Keck and D. G. Nickell, J. Am. Chem. Soc., 102, 3632 (1980).

    Article  CAS  Google Scholar 

  13. G. E. Keck and R. R. Webb, II, J. Org. Chem., 47, 1302 (1982).

    Article  CAS  Google Scholar 

  14. J. E. Boldwin, P. D. Bailey, G. Gallacher, K. A. Singleton, and P. M. Wallace, J. Chem. Soc., Chem. Commun., 1049 (1983)

    Google Scholar 

  15. J. E. Baldwin, P. D. Bailey, G. Gallacher, M. Otsuka, K. A. Singleton, and P. M. Wallace, Tetrahedron, 40, 3695 (1984).

    Article  CAS  Google Scholar 

  16. A. Defoin, H. Fritz, G. Geffroy, and J. Streith, Tetrahedron Lett., 27, 4727 (1986).

    Article  CAS  Google Scholar 

  17. H. Iida, Y. Watanabe, and C. Kibayashi, Tetrahedron Lett., 25, 5091 (1984)

    Article  CAS  Google Scholar 

  18. J. Org. Chem., 50, 1818 (1985).

    Google Scholar 

  19. H. Hart, S. K. Ramaswami, and R. Wilier, J. Org. Chem., 44, 1 (1979).

    Article  CAS  Google Scholar 

  20. G. E. Keck and S. A. Fleming, Tetrahedron Lett., 4736 (1978).

    Google Scholar 

  21. D. L. J. Clive, V. Farina, A. Singh, C. K. Wong, W. A. Kiel, and S. M. Menchen, J. Org. Chem., 45, 2120 (1980)

    Article  CAS  Google Scholar 

  22. K. E. Harding and S. R. Burks, Ibid., 46, 3920 (1981), 49, 40 (1984).

    Google Scholar 

  23. S. Danishefsky, E. Taniyama, and R. R. Webb, II, Tetrahedron Lett., 24, 11 (1983).

    Article  CAS  Google Scholar 

  24. S. R. Johns, J. A. Lamberton, A. A. Sioumis, Aus. J. Chem., 24, 2399 (1971).

    CAS  Google Scholar 

  25. G. E. Keck, Tetrahedron Lett., 4767 (1978).

    Google Scholar 

  26. J. W. Daly, G. B. Brown, M. Mensah-Dwumah, and C. W. Myers, Toxicon, 16, 163 (1978).

    Article  PubMed  CAS  Google Scholar 

  27. Th. F. Spande, J. W. Daly, D. J. Hart, Y.-M. Tsai, T. L. Macdonald, Experientia, 37, 163 (1981).

    Article  Google Scholar 

  28. For syntheses of gephyrotoxin 223AB, see: T. L. Macdonald, J. Org. Chem., 45, 193 (1980).

    Article  CAS  Google Scholar 

  29. J. Royer and H. -P. Husson, Tetrahedron Lett., 26, 1515 (1985).

    Article  CAS  Google Scholar 

  30. C. A. Broka and K. K. Eng, J. Org. Chem., 51, 5045 (1986).

    Article  Google Scholar 

  31. R. V. Stevens and A. W. M. Lee, J. Chem. Soc., Chem. Commun., 133 (1982).

    Google Scholar 

  32. D. J. Hart and Y.-M. Tsai, J. Org. Chem., 47, 4403 (1982).

    Article  CAS  Google Scholar 

  33. H. Iida, Y. Watanabe, and C.Kibayashi, J. Am. Chem. Soc., 107, 5535 (1985).

    Article  Google Scholar 

  34. Refs. 16 and 17. For unpublished syntheses of 42 and a complehensive review in this area, see: J. W. Daly and Th. F. Spande in “The Alkaloids II: Chemical and Biological Perspectives, ” S. W. Pelletier, Ed., Wiley-Interscience, New York, 1986, Vol. 4, Chapter 1.

    Google Scholar 

  35. F. J. Ritter, T. E. M. Rotgens, E. Talman, P. E. J. Verwiel, and F. Stein, Experientia, 29, 530 (1973)

    Article  CAS  Google Scholar 

  36. F. J. Ritter and C. J. Persoons, Neth. J. Zool., 25, 261 (1975).

    Article  CAS  Google Scholar 

  37. J. E. Oliver and P. E. Sonnet, J. Org. Chem., 39, 2662 (1974).

    Article  CAS  Google Scholar 

  38. P. E. Sonnet and J. E. Oliver, J. Heterocycl. Chem., 12, 289 (1975).

    Article  CAS  Google Scholar 

  39. P. E. Sonnet, D. A. Natzel, and R. Mendoza, Ibid., 16, 1040 (1980).

    Google Scholar 

  40. R. V. Stevens and A. W. M. Lee, J. Chem. Soc., Chem. Commun., 102 (1982).

    Google Scholar 

  41. R. Yamaguchi, E. Hata, T. Matsuki, and M. Kawanishi, J. Org. Chem., 52, 2049 (1987).

    Google Scholar 

  42. J. Royer and H.-P. Husson, J. Org. Chem., 50, 670 (1985).

    Article  CAS  Google Scholar 

  43. Y. Moriyama, D.-D. Huynh, C. Monneret, and Q.-K. Huu, Tetrahedron Lett., 825 (1977).

    Google Scholar 

  44. Unpublished results from C. Kibayashi and Y. Watanabe.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-03, Japan

    Chihiro Kibayashi

Authors
  1. Chihiro Kibayashi
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. HEJ Research Institute of Chemistry, University of Karachi, Karachi-32, Pakistan

    Atta-ur-Rahman

  2. Department of Chemistry, Northeastern University, 360 Huntington Avenue, Boston, MA, 02115, USA

    Philip William Le Quesne

Rights and permissions

Reprints and permissions

Copyright information

© 1988 Springer-Verlag Berlin Heidelberg

About this paper

Cite this paper

Kibayashi, C. (1988). Total Synthesis of Nitrogen-Containing Natural Products via Nitroso Diels-Alder Reaction. In: Atta-ur-Rahman, Le Quesne, P.W. (eds) Natural Products Chemistry III. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-74017-6_8

Download citation

  • DOI: https://doi.org/10.1007/978-3-642-74017-6_8

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-74019-0

  • Online ISBN: 978-3-642-74017-6

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation