Amaroxocanes A and B: Sulfated dimeric sterols defend the caribbean coral reef sponge Phorbas amaranthus from fish predators

Journal of Natural Products

Volumn 72, Issue 2, 2009, Pages 259-264

  Morinaka, Brandon I ^a   Pawlik, Joseph R ^c   Molinski, Tadeusz F ^a,b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CALIFORNIA SAN DIEGO   (United States)

^c UNIVERSITY OF NORTH CAROLINA WILMINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMAROXOCANE A; AMAROXOCANE B; STEROL DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL STRUCTURE; CORAL REEF; FEEDING ECOLOGY; FISH; HETERONUCLEAR MULTIPLE BOND CORRELATION; HETERONUCLEAR SINGLE QUANTUM COHERENCE; ISOLATION PROCEDURE; NONHUMAN; NUCLEAR OVERHAUSER EFFECT; PHORBAS AMARANTHUS; PREDATOR; SPONGE (PORIFERA); SYNTHESIS; UNITED STATES;

ANIMALS; FEEDING BEHAVIOR; FISHES; MOLECULAR STRUCTURE; PORIFERA; STEROLS; SULFURIC ACID ESTERS;

ANTHOZOA; PHORBAS AMARANTHUS; THALASSOMA BIFASCIATUM; THALASSOMA LUCASANUM;

EID: 62649128998     PISSN: 01633864     EISSN: None     Source Type: Journal    
DOI: 10.1021/np800652v     Document Type: Article

References (37)

1. Pawlik, J. R.; Chanas, B.; Toonen, R. J.; Fenical, W. Mar. Ecol.: Prog. Ser. 1995, 127, 183-194.
2. Assmann, M.; Lichte, E.; Pawlik, J. R.; Köck, M. Mar. Ecol: Prog. Ser. 2000, 207, 255-262.
3. Wilson, D. M.; Puyana, M.; Fenical, W.; Pawlik, J. R. J. Chem. Ecol. 1999, 25, 2811-2823.
4. Kubanek, J.; Pawlik, J. R.; Eve, T. M.; Fenical, W. Mar. Ecol.: Prog. Ser. 2000, 207, 69-77.
5. Albrizio, S.; Ciminiello, P.; Fattorusso, E.; Magno, S.; Pawlik, J. R. J. Nat. Prod. 1995, 58, 647-652.
6. Masuno, M. N.; Pawlik, J. R.; Molinski, T. F. J. Nat. Prod. 2004, 67, 731-733.
7. Tischler, M.; Ayer, S. W.; Anderson, R. J.; Mitchell, J. F.; Clardy, J. Can. J. Chem. 1988, 66, 1173-1178.
8. Morinaka, B. I.; Masuno, M. N.; Pawlik, J. R.; Molinski, T. F. Org. Lett. 2007, 9, 5219-5222.
9. Amaroxocane A and B each constituted ∼25% of this antifeedant fraction based on HPLC analysis.
10. 13C chemical shifts for the western hemisphere of hamigerol B: δ 79.4, d, C-2; 73.2, d, C-3; 74.6, d, C-6. See ref 21.
11. Newmark, R. A.; Hill, J. R. Org. Magn. Reson. 1980, 13, 40-44.
12. H-22 appeared as a doublet of a doublet, coupled only to the adjacent diastereotopic methylene group (H-23). No cross-peaks were observed between H-20 and H-22 in the COSY or TOCSY spectra.
13. Mass spectra and NMR of these minor constituents showed they are most likely double-bond isomers with sulfate groups at the same or different positions.
14. Kubanek, J.; Pawlik, J. R.; Fenical, W. Nat. Prod. Lett. 2001, 15, 275-285.
15. Jones, A. C.; Blum, J. E.; Pawlik, J. R. J. Exp. Mar. Biol. 2005, 322, 67-81.
16. (a) Pettit, G. R.; Inoue, M.; Kamano, Y.; Herald, D. L.; Arm, C.; Dufresne, C.; Christie, N. D.; Schmidt, J. M.; Doubek, D. L.; Krupa, T. S. J. Am. Chem. Soc. 1988, 110, 2006-2007.
17. (b) Pettit, G. R.; Inoue, M.; Kamano, Y.; Dufresne, C.; Christie, N. D.; Niven, M. L.; Herald, D. L. J. Chem. Soc., Chem. Commun. 1988, 865-867.
18. (c) Pettit, G. R.; Kamano, Y.; Dufresne, C.; Inoue, M.; Christie, N. D.; Schmidt, J. M.; Doubek, D. L. Can. J. Chem. 1989, 67, 1509-1513.
19. (d) Pettit, G. R.; Kamano, Y.; Inoue, M.; Dufresne, C.; Boyd, M. R.; Herald, C. L.; Schmidt, J. M.; Doubek, D. L.; Christie, N. D. J. Org. Chem. 1992, 57, 429-431.
20. (e) Pettit, G. R.; Xu, J. P.; Williams, M. D.; Christie, N. D.; Doubek, D. L.; Schmidt, J. M.; Boyd, M. R. J. Nat. Prod. 1994, 57, 52-63.
21. (f) Pettit, G. R.; Ichihara, Y.; Xu, J. P.; Boyd, M. R.; Williams, M. D. Bioorg. Med. Chem. Lett. 1994, 4, 1507-1512.
22. (g) Pettit, G. R.; Xu, J. P.; Ichihara, Y.; Williams, M. D. Can. J. Chem. 1994, 72, 2260-2267.
23. (h) Pettit, G. R.; Xu, J. P.; Schmidt, J. M. Bioorg. Med. Chem. Lett. 1995, 5, 2027-2032.
24. (i) Pettit, G. R.; Tan, R.; Xu, J. P.; Ichihara, Y.; Williams, M. D.; Boyd, M. R. J. Nat. Prod. 1998, 61, 955-958.
25. (a) Fukuzawa, S.; Matsunaga, S.; Fusetani, N. J. Org. Chem. 1994, 59, 6164-6166.
26. (b) Fukuzawa, S.; Matsunaga, S.; Fusetani, N. J. Org. Chem. 1995, 60, 608-614.
27. (c) Fukuzawa, S.; Matsunaga, S.; Fusetani, N. Tetrahedron 1995, 51, 6707-6716.
28. (d) Fukuzawa, S.; Matsunaga, S.; Fusetani, N. J. Org. Chem. 1997, 62, 4484-4491.
29. Kobayashi, M.; Kawazoe, K.; Kator, T.; Kitagawa, I. Chem. Pharm. Bull. 1992, 40, 1773-1780.
30. Inouye, Y.; Sugo, Y.; Kusumi, T.; Fusetani, N. Chem. Lett. 1994, 419-420.
31. (a) D'Auria, M. V.; Giannini, C.; Zampella, A.; Minale, L.; Debitus, C.; Roussakis, C. J. Org. Chem. 1998, 63, 7382-7388.
32. (b) Zampella, A.; Giannini, C.; D'Auria, M. V.; Debitus, C.; Roussakis, C. Eur. J. Org. Chem. 1999, 949-953.
33. (c) Giannini, C.; Zampella, A.; Debitus, C.; Menou, J. L.; Roussakis, C.; D'Auria, M. V. Tetrahedron 1999, 55, 13749-13756.
34. Cheng, J.-F.; Lee, J.-S.; Sun, F.; Jares-Erijman, E. A.; Cross, S.; Rinehart, K. L. J. Nat. Prod. 2007, 70, 1195-1199.
35. Crellastatins K and M contain different bridging oxabicycles.
36. Hassan, W.; Edrada, R.; Ebel, R.; Wray, V.; Proksch, P. Mar. Drugs 2004, 2, 88-100.
37. These hypothetical reactions for oxidative dimerization at the side chains account for the heterocycles in most of this family of dimeric sulfated sterols; however, alternate mechanisms may be drawn that trigger the cascade with initial formation of the carbocyclic rings in 7 and crellastatin M, respectively.