Skip to main content
SpringerLink
Log in

Studies toward the synthesis of the shark repellent pavoninin-5

  • Published:
Lipids

Abstract

Sharks are the most dangerous predators of people in the sea, resulting in people being mauled and killed each year. A shark repellent could help to diminish this danger. The aglycone of the shark repellent pavoninin-5, (25R)-cholest-5-en-3β,15α,26-triol (5a), was synthesized from diosgenin (9). Removing mercury from the Clemmensen reduction of 9 gave a higher yield of (25R)-cholest-5-en-3β,16β,26-triol, 10a, and was also more environmentally friendly. Attempted methods for the transposition of the C-16β hydroxyl to the 15α position are described. A successful method for this transposition via the 15α-hydroxy-16-ketone, 8a, using the Barton deoxygenation reaction on the 16-alcohol 14b, is reported.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Abbreviations

MEM:

methoxyethoxymethyl

TBDMS:

tert-butyldimethylsilyl

References

  1. Yasumoto, T., and Murata, M. (1993) Marine Toxins, Chem. Rev. 93, 1897–1909.

    Article  CAS  Google Scholar 

  2. Pawlik, J.R. (1993) Marine Invertebrate Chemical Defenses, Chem. Rev. 93, 1911–1922.

    Article  CAS  Google Scholar 

  3. Oren, Z., and Shai, Y. (1996) A Class of Highly Potent Antibacterial Peptides Derived from Pardaxin, a Pore-forming Peptide Isolated from Moses Sole Fish Pardachirus marmoratus, Eur. J. Biochem. 66, 6389–6393.

    Google Scholar 

  4. Tachibana, K., Sakaitani, M., and Nakanishi, K. (1985) Pavoninins, Shark-Repelling and Ichthyotoxic Steroid N-Acetylglucosamides from the Defense Secretion of the Sole Pardachirus pavoninus (Soleidae), Tetrahedron 41, 1027–1037.

    Article  CAS  Google Scholar 

  5. Ohnishi, Y., and Tachibana, K. (1997) Synthesis of Pavoninin-1, a Shark Repellent Substance, and Its Structural Analogues Toward Mechanistic Studies on Their Membrane Perturbation, Bioorg. Med. Chem. 5, 2251–2265.

    Article  PubMed  CAS  Google Scholar 

  6. Kim, H.S., Kim, I.C., and Lee, S.O. (1997) Synthesis of Two Marine Natural Products: The Aglycones of Pavoninin-1 and 2, Tetrahedron 53, 8129–8136.

    Article  CAS  Google Scholar 

  7. Marker, R.E., and Turner, D.L. (1941) Sterols CXV. Sapogenins XLIV. The Relation Between Diosgenin and Cholesterol. J. Am. Chem. Soc. 63, 767–771.

    Article  CAS  Google Scholar 

  8. Williams, J.R., Chai, D., and Wright, D. (2002) Synthesis of (25R)-26-Hydroxycholesterol, Steroids 67, 1041–1044.

    Article  PubMed  CAS  Google Scholar 

  9. Kim, H.S., Wilson, W.K., Needleman, D.H., Pinkerton, F.D., Wilson, D.K., Quiocho, F.A., and Schroepfer, G.J. Jr. (1989) Inhibitors of Sterol Synthesis. Chemical Synthesis, Structure, and Biological Activities of (25R)-3β,26-Dihydroxy-5α-cholest-8(14)-en-15-one, a Metabolite of 3β-Hydroxy-5α-cholest-8(14)-en-15-one, J. Lipid Res. 30, 247–261.

    PubMed  CAS  Google Scholar 

  10. Davis, F.A., Billmers, J.M., Gosciniak, D.J., Towson, J.C., and Bach, R.D. (1986) Chemistry of Oxaziridines. 7. Kinetics and Mechanism of the Oxidation of Sulfoxides and Alkenes by 2-Sulfonyloxaziridines. Relationship to the Oxygen-Transfer Reactions of Metal Peroxides, J. Org. Chem. 51, 4240–4245.

    Article  CAS  Google Scholar 

  11. Davis, F.A., Towson, J.C., Weismiller, M.C., Lal, S., and Carroll, P.J. (1988) Chemistry of Oxaziridines. 11. (Camphorylsulfonyl)oxaziridine: Synthesis and Properties. J. Am. Chem. Soc. 110, 8477–8482.

    Article  CAS  Google Scholar 

  12. Adam, W., Chan, Y.Y., Cremer, D., Gauss, J., Scheutzow, D., and Schindler, M. (1987) Spectral and Chemical Properties of Dimethyldioxirane as Determined by Experiment and ab initio Calculations, J. Org. Chem. 52, 2800–2803.

    Article  CAS  Google Scholar 

  13. Guertin, K.R., and Chan, T.-H. (1991) Facile Synthesis of α-Hydroxy Carbonyl Compounds by Enolate Oxidation with Dimethyldioxirane, Tetrahedron Lett. 32, 715–718.

    Article  CAS  Google Scholar 

  14. Corey, E.J., and Gross, A.W. (1984) Highly Selective, Kinetically Controlled Enolate Formation Using Lithium Dialkylamides in the Presence of Trimethylchlorosilane, Tetrahedron Lett. 25, 495–498.

    Article  CAS  Google Scholar 

  15. Barton, D.H.R., and McCombie, S.W. (1975) New Method for the Deoxygenation of Secondary Alcohols, J. Chem. Soc., Perkin Trans., 1, 16, 1574–1585.

    Article  Google Scholar 

  16. Niwa, H., Hida, T., and Yamada, K. (1981) A New Method for Cleavage of Aliphatic Methyl Ethers, Tetrahedron Lett. 22, 4239–4240.

    Article  CAS  Google Scholar 

  17. Corey, E.J., Gras, J.L., and Ulrich, P. (1976) A New General Method for Protection of the Hydroxyl Function, Tetrahedron Lett. 11, 809–812.

    Article  Google Scholar 

  18. Guindon, Y., Yoakim, C., and Morton, H.E. (1984) Dimethylboron Bromide and Diphenylboron Bromide: Cleavage of Acetals and Ketals, J. Org. Chem. 49, 3912–3920.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Temple University, 13 & Norris Sts., 19122-2585, Philadelphia, PA

    John R. Williams, Deping Chai, Hua Gong, Wei Zhao & Dominic Wright

Authors
  1. John R. Williams
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Deping Chai
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hua Gong
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dominic Wright
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to John R. Williams.

About this article

Cite this article

Williams, J.R., Chai, D., Gong, H. et al. Studies toward the synthesis of the shark repellent pavoninin-5. Lipids 37, 1193–1195 (2002). https://doi.org/10.1007/s11745-002-1020-1

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11745-002-1020-1

Keywords

Search

Navigation