Sesquiterpene Lactones, Acyl Phenyl Propanoids and Other Constituents from Schkuhria pinnata var. wislizeni. Antioxidant Evaluation
DOI:
https://doi.org/10.29356/jmcs.v53i3.1002Keywords:
Asteraceae, Schkuhria pinnata var, wislizeni, 1,13dehydroeriolin, dischkuhriolin, 14-O-schkuhridin B, flavonoids, acyl phenyl propane, antioxidant activityAbstract
Chemical investigation of aerial parts of Schkuhria pinnata var wislizeni (Asteraceae) allowed the characterization of the sesquiterpene lactones 1, 2 and 5, the flavonoids 3 and 4, and the acyl phenyl propanoids 10 and 11. Structure 2, named dischkuhriolin, was confirmed as a Diels Alder adduct of 1 as dienophile and a guaianolide as diene. Spectroscopic analysis of 5 and its diacetyl derivative allowed the structural correction of compounds previously reported from Schkuhria. 2, 10 and 11 are new natural compounds. Biological assays indicated that the mixture 10 + 11 showed antioxidant activity expressed as inhibition of AAPH-induced damage in rat pancreatic homogenate.
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References
1. Heiser, Ch. B. Ann. Miss. Bot. Gar. 1945, 32, 265-277.
2. Rydberg, P. A. North American Flora 1914, 34, 44-47.
3. McVaugh, R. Fl. Novo-Galiciana 1984, 12, 794-799.
4. Turner, B. L. Phytologia 1995, 79, 364-368.
5. http://www.ars-grin.gov/cgi-bin/npgs/html/taxon.pl?413435.
6. Martínez, M. Las Plantas Medicinales de México, Ed. Botas. 1954.
7. Bascope, M.; Sterner, O. Rev. Bol. Quím. 2007, 24, 14-25. von Koenen, E. Medicinal, Poisonous, and Edible Plants in Namibia. Klaus Hess Publishers. Verlag. 2001. Deutschländer, M.S.; van de Venter, M.; Roux, J.L.; Lall, N. J. Ethnopharmacol. 2009, 124, 619-624. Muthaura, C.N.; Rukunga, G.M.; Chhabra, S.C.; Omar, S.A.; Guantai, A.N.; Gathirwa, J.W.; Tolo, F.M.; Mwitari, P.G.; Keter, L.K.; Kirira, P.G.; Kimani, C.W.; Mungai, G.M.; Njagi, E.N.M. Phytotherapy Research 2007, 21, 860-867.
8. Luseba, D.; Elgorashi, E. E.; Ntloedibe, D. T.; Van Staden, J. South Afr. J. Bot. 2007, 73, 378-383.
9. Bohlmann, F.; Zdero, Ch. Phytochemistry 1977, 16, 780-781.
10. Bohlmann, F.; Jakupovic, J.; Robinson, H.; King, R. Phytochemistry 1980, 19, 881-884.
11. Herz, W.; Govindan, S. Phytochemistry 1980, 19, 1234-1236.
12. Pettei, M. J.; Miura, Y.; Kubo, Y.; Nakanishi, K. Heterocycles 1978, 11, 471-480.
13. Delgado, G.; Hernández, H.; Romo de Vivar, A. J. Org. Chem. 1984, 49, 2994-2996.
14. Pérez, A. L.; Mendoza, J. S.; Romo de Vivar, A. Phytochemistry 1984, 23, 2911-2913.
15. Delgado, G.; Tejeda V. Nat. Prod. Lett. 1998, 12, 17-22.
16. Delgado, G.; Tejeda, V.; Salas, A.; Chávez, M. I.; Guzmán, S.; Bolaños, A.; Aguilar, M. I.; Navarro, V.; Villarreal, M. L. J. Nat. Prod. 1998, 61, 1082-1085.
17. García, A.; Delgado, G. Helv. Chim. Acta 2006, 89, 16-29. Cano, A.; Espinoza, M.; Ramos, C. H.; Delgado, G. J. Mex. Chem. Soc. 2006, 50, 71-75.
18. Villaseñor Ríos, J. L.; Espinosa García, F. J. Catálogo de Malezas de México. Universidad Nacional Autónoma de México y Fondo de Cultura Económica. 1998. Espinosa García, F. J.; Sarukhán, J. Manual de Malezas del Valle de México. Universidad Nacional Autónoma de México y Fondo de Cultura Económica. 1997.
19. Romo de Vivar, A.; Pérez, A. L.; León, C.; Delgado, G. Phytochemistry 1982, 21, 2905-2908.
20. Calderón, J. S.; Quijano, L.; Gómez-Garibay, F.; Sánchez, D. M.; Rios, T.; Fronczek, F. R. Phytochemistry 1987, 26, 1747-1750.
21. Hase, T.; Ohtani, K.; Kasai, R.; Yamasaki, K.; Picheansoonthon, C. Phytochemistry 1995, 40, 287-290.
22. Iwashina, T.; Kamenosono, K.; Ueno, T. Phytochemistry 1999, 51, 1109-1111.
23. Woodhead, S.; Galeffi, C.; Bettolo, G. B. M. Phytochemistry 1982, 21, 455-456.
24. Stewart, E.; Mabry, T. J. Phytochemistry 1985, 24, 2731-2732.
25. Samek, Z.; Harmatha, J. Coll. Czech. Chem. Commun. 1978, 43, 2779-2799.
26. The hypothetical 1(2),4(5)-H10α-guaiadienolide (i) could be formed from the same intermediate that would produce 11,13dehydroeriolin (1), namely, the 4(5)-epoxy-germacrolide (ii, 4α,5β-epoxy-8-epi-inunolide) [20]. The transannular reaction could afford the cation iii, and the stabilization of the reactive intermediate and dehydration can produce i.
27. Fragments A and B (Fig. 1, derived from an endo approach in the Diels Alder reaction) have the sesquiterpene residues with an extended arrangement, in contrast with the exo approach (fragments C and D, Fig. 1) that produce stacked arrangement of the sesquiterpene fragments.
28. X-ray analysis data for compound 2. All data were collected on Brucker Smart Apex CCD diffractometer using 1.93 to 25.02 θ at 293(2) K. The refinement methods was full-matrix least squares on F 2. C30H38O6; M = 494.60; crystal system monoclinic; space group P21; a = 11.162(1) Å; b = 8.6749(5) Å; c = 14.221(1) Å; α = 90°; β = 109.018(1)°; γ = 90°; V = 1301.8(1) Å3; Z = 2; Dx = 1.262 Mgm-3; M = 0.087 mm-1; F(000) = 532; crystal size 0.418 × 0.274 ´ 0.100; colorless prism. Index ranges -13 ≤ h ≤ 13, -10 ≤ k ≤ 10, -16 ≤ l ≤ 16. 10765 reflections were collected and 4577 [R(int) = 0.0558] reflections were independents. Completeness to θ = 25.02° 99.9%; final R indices [I > 2σ (I)] R1 = 0.0449, wR2 = 0.0547; R indices (all data) R1 = 0.0808, wR2 = 0.0616; Largest diff. peak and hole were 0.119 and -0.129 e Å-3. CCDC-753938 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc. cam.ac.uk/data_request/cif.
29. Delgado, G.; Guzmán, S.; Romo de Vivar, A. Phytochemistry 1987, 26, 755-759.
30. The species identified as Schkuhria anthemoidea var. wislizeni (Gray) Heiser analyzed by Mabry [24] should be considered as Schkuhria pinnata (Lam.) Kuntze var. wislizeni (A. Gray) B. L. Turner, according to Turner [4]. This is supported by the chemical constituents reported in this contribution. It is interesting to note that 11,13-dehydroeriolin (1) may be considered as a typical secondary metabolite of the species now identified as S. pinnata var. wislizeni. The original reports informing this substance as a constituent of Schkuhria schkuhrioides [13, 19] could be considered for further confirmation, since subsequent analyses for this last species [15, 16] did not afford this sesquiterpene lactone.
31. Chen, Ch.-Y.; Shen, Y.-Ch.; Chen, Y.-J-; Shen, J.-H.; Duh, CH.-Y. J. Nat. Prod. 1999, 62, 573-576.
32. Su, W.-Ch.; Fang, J.-M.; Cheng, Y.-Sh. Phytochemistry 1995, 40, 563-566.
33. Soto, C.; Recoba, R.; Barrón, H.; Álvarez, C.; Favari, L. Comp. Biochem. Physiol. 2003, 136C, 205212.
34. Quine, S. D.; Raghu, P. S. Pharmacol. Rep. 2005, 57, 610-615.
35. Narváez-Mastache, J. M.; Soto, C.; Delgado, G. Biol. Pharm. Bull. 2007, 30, 1503-1510.
36. Ohkawa, H.; Ohishi, N.; Yagi, K. Anal. Biochem. 1979, 95, 351358.
37. Coll, J. C.; Bowden, B. F. J. Nat. Prod. 1986, 49, 934-936
38. Narváez-Mastache, J. M.; Novillo, F.; Delgado, G. Phytochemistry 2008, 69, 451-456.
2. Rydberg, P. A. North American Flora 1914, 34, 44-47.
3. McVaugh, R. Fl. Novo-Galiciana 1984, 12, 794-799.
4. Turner, B. L. Phytologia 1995, 79, 364-368.
5. http://www.ars-grin.gov/cgi-bin/npgs/html/taxon.pl?413435.
6. Martínez, M. Las Plantas Medicinales de México, Ed. Botas. 1954.
7. Bascope, M.; Sterner, O. Rev. Bol. Quím. 2007, 24, 14-25. von Koenen, E. Medicinal, Poisonous, and Edible Plants in Namibia. Klaus Hess Publishers. Verlag. 2001. Deutschländer, M.S.; van de Venter, M.; Roux, J.L.; Lall, N. J. Ethnopharmacol. 2009, 124, 619-624. Muthaura, C.N.; Rukunga, G.M.; Chhabra, S.C.; Omar, S.A.; Guantai, A.N.; Gathirwa, J.W.; Tolo, F.M.; Mwitari, P.G.; Keter, L.K.; Kirira, P.G.; Kimani, C.W.; Mungai, G.M.; Njagi, E.N.M. Phytotherapy Research 2007, 21, 860-867.
8. Luseba, D.; Elgorashi, E. E.; Ntloedibe, D. T.; Van Staden, J. South Afr. J. Bot. 2007, 73, 378-383.
9. Bohlmann, F.; Zdero, Ch. Phytochemistry 1977, 16, 780-781.
10. Bohlmann, F.; Jakupovic, J.; Robinson, H.; King, R. Phytochemistry 1980, 19, 881-884.
11. Herz, W.; Govindan, S. Phytochemistry 1980, 19, 1234-1236.
12. Pettei, M. J.; Miura, Y.; Kubo, Y.; Nakanishi, K. Heterocycles 1978, 11, 471-480.
13. Delgado, G.; Hernández, H.; Romo de Vivar, A. J. Org. Chem. 1984, 49, 2994-2996.
14. Pérez, A. L.; Mendoza, J. S.; Romo de Vivar, A. Phytochemistry 1984, 23, 2911-2913.
15. Delgado, G.; Tejeda V. Nat. Prod. Lett. 1998, 12, 17-22.
16. Delgado, G.; Tejeda, V.; Salas, A.; Chávez, M. I.; Guzmán, S.; Bolaños, A.; Aguilar, M. I.; Navarro, V.; Villarreal, M. L. J. Nat. Prod. 1998, 61, 1082-1085.
17. García, A.; Delgado, G. Helv. Chim. Acta 2006, 89, 16-29. Cano, A.; Espinoza, M.; Ramos, C. H.; Delgado, G. J. Mex. Chem. Soc. 2006, 50, 71-75.
18. Villaseñor Ríos, J. L.; Espinosa García, F. J. Catálogo de Malezas de México. Universidad Nacional Autónoma de México y Fondo de Cultura Económica. 1998. Espinosa García, F. J.; Sarukhán, J. Manual de Malezas del Valle de México. Universidad Nacional Autónoma de México y Fondo de Cultura Económica. 1997.
19. Romo de Vivar, A.; Pérez, A. L.; León, C.; Delgado, G. Phytochemistry 1982, 21, 2905-2908.
20. Calderón, J. S.; Quijano, L.; Gómez-Garibay, F.; Sánchez, D. M.; Rios, T.; Fronczek, F. R. Phytochemistry 1987, 26, 1747-1750.
21. Hase, T.; Ohtani, K.; Kasai, R.; Yamasaki, K.; Picheansoonthon, C. Phytochemistry 1995, 40, 287-290.
22. Iwashina, T.; Kamenosono, K.; Ueno, T. Phytochemistry 1999, 51, 1109-1111.
23. Woodhead, S.; Galeffi, C.; Bettolo, G. B. M. Phytochemistry 1982, 21, 455-456.
24. Stewart, E.; Mabry, T. J. Phytochemistry 1985, 24, 2731-2732.
25. Samek, Z.; Harmatha, J. Coll. Czech. Chem. Commun. 1978, 43, 2779-2799.
26. The hypothetical 1(2),4(5)-H10α-guaiadienolide (i) could be formed from the same intermediate that would produce 11,13dehydroeriolin (1), namely, the 4(5)-epoxy-germacrolide (ii, 4α,5β-epoxy-8-epi-inunolide) [20]. The transannular reaction could afford the cation iii, and the stabilization of the reactive intermediate and dehydration can produce i.
27. Fragments A and B (Fig. 1, derived from an endo approach in the Diels Alder reaction) have the sesquiterpene residues with an extended arrangement, in contrast with the exo approach (fragments C and D, Fig. 1) that produce stacked arrangement of the sesquiterpene fragments.
28. X-ray analysis data for compound 2. All data were collected on Brucker Smart Apex CCD diffractometer using 1.93 to 25.02 θ at 293(2) K. The refinement methods was full-matrix least squares on F 2. C30H38O6; M = 494.60; crystal system monoclinic; space group P21; a = 11.162(1) Å; b = 8.6749(5) Å; c = 14.221(1) Å; α = 90°; β = 109.018(1)°; γ = 90°; V = 1301.8(1) Å3; Z = 2; Dx = 1.262 Mgm-3; M = 0.087 mm-1; F(000) = 532; crystal size 0.418 × 0.274 ´ 0.100; colorless prism. Index ranges -13 ≤ h ≤ 13, -10 ≤ k ≤ 10, -16 ≤ l ≤ 16. 10765 reflections were collected and 4577 [R(int) = 0.0558] reflections were independents. Completeness to θ = 25.02° 99.9%; final R indices [I > 2σ (I)] R1 = 0.0449, wR2 = 0.0547; R indices (all data) R1 = 0.0808, wR2 = 0.0616; Largest diff. peak and hole were 0.119 and -0.129 e Å-3. CCDC-753938 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc. cam.ac.uk/data_request/cif.
29. Delgado, G.; Guzmán, S.; Romo de Vivar, A. Phytochemistry 1987, 26, 755-759.
30. The species identified as Schkuhria anthemoidea var. wislizeni (Gray) Heiser analyzed by Mabry [24] should be considered as Schkuhria pinnata (Lam.) Kuntze var. wislizeni (A. Gray) B. L. Turner, according to Turner [4]. This is supported by the chemical constituents reported in this contribution. It is interesting to note that 11,13-dehydroeriolin (1) may be considered as a typical secondary metabolite of the species now identified as S. pinnata var. wislizeni. The original reports informing this substance as a constituent of Schkuhria schkuhrioides [13, 19] could be considered for further confirmation, since subsequent analyses for this last species [15, 16] did not afford this sesquiterpene lactone.
31. Chen, Ch.-Y.; Shen, Y.-Ch.; Chen, Y.-J-; Shen, J.-H.; Duh, CH.-Y. J. Nat. Prod. 1999, 62, 573-576.
32. Su, W.-Ch.; Fang, J.-M.; Cheng, Y.-Sh. Phytochemistry 1995, 40, 563-566.
33. Soto, C.; Recoba, R.; Barrón, H.; Álvarez, C.; Favari, L. Comp. Biochem. Physiol. 2003, 136C, 205212.
34. Quine, S. D.; Raghu, P. S. Pharmacol. Rep. 2005, 57, 610-615.
35. Narváez-Mastache, J. M.; Soto, C.; Delgado, G. Biol. Pharm. Bull. 2007, 30, 1503-1510.
36. Ohkawa, H.; Ohishi, N.; Yagi, K. Anal. Biochem. 1979, 95, 351358.
37. Coll, J. C.; Bowden, B. F. J. Nat. Prod. 1986, 49, 934-936
38. Narváez-Mastache, J. M.; Novillo, F.; Delgado, G. Phytochemistry 2008, 69, 451-456.
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