Hypargyrin A, a Hemiacetalic Germacrolide from Viguiera hypargyrea (Asteraceae). Biogenetic Implications and Biological Evaluation
Keywords:
Asteraceae, Viguiera hypargyrea, sesquiterpene lactones, germacrolides, hypargyrin A, budlein B, biogenesis, anti-inflammatory activity, cytotoxic activityAbstract
A new hemiacetalic germacrolide 6, named hypargyrin A, was isolated from the aerial parts of Viguiera hypargyrea, along with the known compounds (8R,9R)-β-caryophyllene epoxide, entkaur-16-en-19-oic acid (1), hispidulin (2), 8β-epoxyangeloyloxy-14-acetoxy-tithifolin (3), 8β-epoxyangeloyloxy-14-hydroxy-tithifolin (4) and budlein B (5). Spectroscopic analysis of 6 allowed the structural correction of a compound isolated from Blainvillea gayana. Budlein B (5) can be considered the biogenetic precursor of 6, and two pathways for its formation are proposed. Hypargyrin A (6) did not display significant anti-inflammatory activity against ear edema in mice induced by TPA, but showed cytotoxic activity against HeLa (IC50 35.1 μM) and Hep-2 (39.2 μM) human cells.
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References
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2. a) Romo de Vivar, A.; Delgado, G. Bol. Soc. Chil. Quím. 1985, 30, 79-100. b) Ambrosio, S. R.; Tirapelli, C. R.; da Costa, F. B.; de Oliveira, A. M. Life Sciences 2006, 79, 925-933
3. Marquina, S.; Maldonado, N.; Garduño-Ramírez, M. L.; Aranda, E.; Villarreal, M. L.; Navarro, V.; Bye, R.; Delgado, G.; Álvarez, L. Phytochemistry 2001, 56, 93-97.
4. Álvarez, L.; Zamilpa, A.; Marquina, S.; González, M. Rev. Soc. Quím. Méx. 2003, 47, 173-177.
5. Zamilpa, A.; Tortoriello, J.; Navarro, V.; Delgado, G.; Alvarez, A. Planta Medica 2002, 68, 281-283.
6. a) Álvarez, L.; Mata, R.; Delgado, G.; Romo de Vivar, A. Phytochemistry 1985, 24, 2973-2976. b) Delgado, G.; Álvarez, L.; Soriano-García, M.; Toscano, R. A.; Mata, R.; Pereda-Miranda, R. J. Nat. Prod. 1987, 50, 273-276.
7. Wollenweber, E.; Doerr, M.; Roitman, J. N.; Schilling, E. Zeit. Naturfor. 1995, 50, 588-590.
8. León, A.; Reyes, B. M.; Chávez, M. I.; Toscano, R. A. Delgado, G. J. Mex. Chem. Soc. 2009, 53, 193-200.
9. Heymann, H.; Tezuka, Y.; Kikuchi, T.; Suprityatna, S. Chem. Pharm. Bull. 1994, 42, 138-146.
10. Piozzi, F.; Passannanti, S.; Paternostro, M. P.; Sprio, V. Phytochemistry 1971, 10, 1164-1166.
11. Ferraro, G.; Martino, V.; Borrajo, G.; Coussio, J. D. Phytochemistry 1987, 26, 3092-3093.
12. Bohlmann, F.; Ziesche, J.; Robinson, H.; King, R. M. Phytochemistry 1981, 20, 267-270.
13. a) Romo de Vivar, A.; Guerrero, C.; Díaz, E.; Bratoeff, E. A.; Jiménez, L. Phytochemistry 1976, 15, 525-527. b) Romo de Vivar, A.; Delgado, G.; Guerrero, C.; Reséndiz, J.; Ortega, A. Rev. Latinoamer. Quím. 1978, 9, 171-176. c) Hoeneisen, M.; Silva, M.; Bohlmann, F. Phytochemistry 1980, 19, 2765-2766
14. a) Samek, Z.; Harmatha, J. Coll. Czech. Chem. Commun. 1978, 43, 2779-2799. b) Samek, Z. Tetrahedron 1970, 9, 671-674.
15. Kametani, T.; Yukawa, H.; Suzuki, Y.; Honda, T. J. Chem. Soc., Perkin Trans. 1, 1985, 2151.
16. Kijoa, A.; Bastos, M. S. M.; Gedris, T.; Herz, W. Phytochemistry 1993, 32, 383-385.
17. a) Bohlmann, F.; Ziesche, J.; King, R. M.; Robinson, H. Phytochemistry 1981, 20, 263-266. b) Singh, P.; Sharma, A. K.; Joshi, K. C.; Jakupovic, J.; Bohlmann, F. Phytochemistry 1985, 24, 2023-2028.
18. a) Maragelman, K. M.; Anza Espinar, L.; Sosa, V. E.; Uriburu, M. L.; de la Fuente, J. R. Phytochemistry 1996, 41, 499-502. b) Da Costa, F. B.; Ito, Y.; André, R. F. G.; Vichnewski, W. Fitoterapia 1998, 69, 86-87. Delgado, G.; Álvarez, L.; Romo de Vivar, A. Phytochemistry 1985, 24, 2736-2738.
19. Bohlmann, F.; Ziesche, J.; Robinson, H.; King, R. Phytochemistry 1981, 20, 267-270.
20. Delgado, G.; Guzmán, S. Synlett 1999, 1006-1008.
21. Delgado, G.; Tejeda, V.; Salas, A.; Chávez, M. I.; Guzmán, S.; Bolaños, A.; Aguilar, M. I.; Navarro, V.; Villarreal, M. I. J. Nat. Prod. 1998, 61, 1082-1085.
22. The transformation of a germacrolide to a melampolide has been also previously observed during the characterization of the aldehyde derived from deacetyl gochnatolide [23], which isomerized to 8-epi-schkuhriolide
23. Maldonado, E.; Flores, A. M.; Ortega, A. Phytochemistry 1988, 27, 861-863.
24. Delgado, G.; Álvarez, L.; Guzmán, S. Trends in Organic Chemistry (India) 1995, 5, 1-10
25. Fischer, N. H.; Olivier, N. J.; Fischer, H. D. Progress in the Chemistry of Organic Natural Products. Herz, W.; Griesebach, H.; Kirby, G. W. Eds. Springer-Verlag. Wien, New York. 1979, 38, 47-390.
26. Schmidt, T. J. Curr. Org. Chem. 1999, 3, 577-608.
27. a) Siedle, B.; García-Piñeres, A. J.; Murillo, R.; Schulte-Möntig, J.; Castro, V.; Rüngeler, P.; Klaas, Vh. A.; Da Costa, F.; Kisiel, W.; Merfort, I. J. Med. Chem. 2004, 47, 6042-6054. b) Humar, M.; García-Piñeres, A. J.; Castro, V.; Merfort, I. Biochem. Pharmacol. 2003, 65, 1551-1563.
28. a) Taylor, P. G.; Depuy Loo, O. A.; Bonilla, J. A.; Murillo, R. Fitoterapia 2008, 79, 428-432. b) Nicolete, R.; Arakawa, N. S.; Rius, C.; Nomizo, A.; Jose, P. J.; Da Costa, F.; Sanz, M. J.; Faccioli, L. H. Phytomedicine 2009, 16, 904-915.
29. a) Tubaro, A.; Dri, P.; Delbello, G.; Zilli, C.; Della Logia, R. Agents Actions 1985, 17, 347-349. b) Della Logia, R.; Tubaro, A.; Sosa, S.; Becker, H.; Saar, St.; Isaac, O. Planta Med. 1994, 60, 516-529. c) Delgado, G.; Olivares, M. S.; Chávez, M. I.; Ramírez-Apan, T.; Linares, E.; Bye, R. A.; Espinosa-García, F. J. J. Nat. Prod. 2001, 64, 861-864.
30. a) Monks, A.; Scudiero, D.; Skehan, P.; Shoemaker, R.; Paul, K.; Vistica, D.; Hose, C.; Langley, J.; Cronise, P.; Vaigro-Wolff, A.; Gray-Goodrich, M.; Campbell, H.; Mayo, J.; Boyd, M. J. Natl. Cancer Inst. 1991, 83, 757-766. b) García, A.; Ramírez-Apan, T.; Cogordán, J. A.; Delgado, G. Can. J. Chem. 2006, 84, 1593-1602.
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