Unified synthesis of eudesmanolides, combining biomimetic strategies with homogeneous catalysis and free-radical chemistry

Organic Letters

Volumn 5, Issue 11, 2003, Pages 1935-1938

  Barrero, Alejandro F ^a   Rosales, Antonio ^a   Cuerva, Juan M ^a   Oltra, J Enrique ^a  

^a UNIVERSITY OF GRANADA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

2,4,6 TRIMETHYL 1 TRIMETHYLSILYLPYRIDINIUM CHLORIDE; EUDESMANOLIDE DERIVATIVE; PYRIDINE DERIVATIVE; REAGENT; TITANOCENE; UNCLASSIFIED DRUG; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; EUDESMANOLIDE; FREE RADICAL; SESQUITERPENE;

ARTICLE; BIOMIMETICS; CATALYSIS; DRUG SYNTHESIS; CHEMISTRY; ELECTRON TRANSPORT; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

BIOMIMETICS; CATALYSIS; ELECTRON TRANSPORT; FREE RADICALS; INDICATORS AND REAGENTS; MAGNETIC RESONANCE SPECTROSCOPY; SESQUITERPENES;

EID: 0041350396     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034510k     Document Type: Article

References (38)

1. (a) Fischer, N. H.; Olivier, E. J.; Fischer, H. D. Prog. Chem. Org. Nat. Prod. 1979, 38, 134-165.
2. (b) Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman and Hall, London, 1991; Vol. 1, pp 340-371.
3. (c) Fraga, B. M. Nat. Prod. Rep. 2002, 19, 650-672 and previous issues in this series.
4. (a) Hehner, S. P.; Heinrich, M.; Bork, P. M.; Vogt, M.; Ratter, F.; Lehmann, V.; Schulze-Osthoff, K.; Dröge, W.; Schmitz, M. L. J. Biol. Chem. 1998, 273, 1288-1297.
5. (b) Dirsch, V. M.; Stuppner, H.; Ellmerer-Müller, E. P.; Vollmar, A. M. Bioorg. Med. Chem. 2000, 8, 2747-2753.
6. (c) Skaltsa, H.; Lazari, D.; Panagouleas, C.; Georgiadou, E.; García, B.; Sokovic, M. Phytochemistry 2000, 55, 903-908
7. Some selected examples: (a) Schultz, A. G.; Godfrey, J. D. J. Am. Chem. Soc. 1980, 102, 2414-2428. (b) Blay, G.; Cardona, L.; García, B.; Pedro, J. R. J. Org. Chem. 1993, 58, 7204-7208. (c) Watson, F. C.; Kilburn, J. D. Tetrahedron Lett. 2000, 41, 10341-10345.
8. Some selected examples: (a) Schultz, A. G.; Godfrey, J. D. J. Am. Chem. Soc. 1980, 102, 2414-2428. (b) Blay, G.; Cardona, L.; García, B.; Pedro, J. R. J. Org. Chem. 1993, 58, 7204-7208. (c) Watson, F. C.; Kilburn, J. D. Tetrahedron Lett. 2000, 41, 10341-10345.
9. Some selected examples: (a) Schultz, A. G.; Godfrey, J. D. J. Am. Chem. Soc. 1980, 102, 2414-2428. (b) Blay, G.; Cardona, L.; García, B.; Pedro, J. R. J. Org. Chem. 1993, 58, 7204-7208. (c) Watson, F. C.; Kilburn, J. D. Tetrahedron Lett. 2000, 41, 10341-10345.
10. 3CH; see: (a) Barrero, A. F.; Oltra, J. E.; Barragán, A.; Alvarez, M. J. Chem. Soc., Perkin Trans. 1 1998, 4107-4113. (b) Barrero, A. F.; Oltra, J. E.; Cuerva, J. M.; Rosales, A. J. Org. Chem. 2002, 67, 2566-2571. (c) Barrero, A. F.; Oltra, J. E. ; Alvarez, M.; Rosales, A. J. Org. Chem. 2002, 67, 5461-5469.
11. 3CH; see: (a) Barrero, A. F.; Oltra, J. E.; Barragán, A.; Alvarez, M. J. Chem. Soc., Perkin Trans. 1 1998, 4107-4113. (b) Barrero, A. F.; Oltra, J. E.; Cuerva, J. M.; Rosales, A. J. Org. Chem. 2002, 67, 2566-2571. (c) Barrero, A. F.; Oltra, J. E. ; Alvarez, M.; Rosales, A. J. Org. Chem. 2002, 67, 5461-5469.
12. 3CH; see: (a) Barrero, A. F.; Oltra, J. E.; Barragán, A.; Alvarez, M. J. Chem. Soc., Perkin Trans. 1 1998, 4107-4113. (b) Barrero, A. F.; Oltra, J. E.; Cuerva, J. M.; Rosales, A. J. Org. Chem. 2002, 67, 2566-2571. (c) Barrero, A. F.; Oltra, J. E. ; Alvarez, M.; Rosales, A. J. Org. Chem. 2002, 67, 5461-5469.
13. (a) Barrero, A. F.; Oltra, J. E.; Morales, V.; Álvarez, M. J. Nat. Prod. 1997, 60, 1034-1035.
14. (b) Barrero, A. F.; Oltra, J. E.; Álvarez, M. Tetrahedron Lett. 1998, 39, 1401-1404.
15. For a recent overview on contemporary free-radical chemistry, see: Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; VCH: Weinheim, Germany, 2001; Vols. 1 and 2.
16. RajanBabu, T. V.; Nugent, W. A. J. Am. Chem. Soc. 1994, 116, 986-997.
17. 2 and Mn dust; see: (a) Sekutowski, D.; Jungst, R.; Stucky, G. D. Inorg. Chem. 1978, 17, 1848-1855. (b) Enemaerke, R. J.; Hjollund, G. H.; Daasbjerg, K.; Skrydstrup, T. Compt. Rend. Acad. Sc. II 2001, 4, 435-438.
18. 2 and Mn dust; see: (a) Sekutowski, D.; Jungst, R.; Stucky, G. D. Inorg. Chem. 1978, 17, 1848-1855. (b) Enemaerke, R. J.; Hjollund, G. H.; Daasbjerg, K.; Skrydstrup, T. Compt. Rend. Acad. Sc. II 2001, 4, 435-438.
19. (a) Fürstner, A.; Hupperts, A. J. Am. Chem. Soc. 1995, 117, 4468-4475.
20. (b) Gansäuer, A.; Bluhm, H.; Pierobon, M. J. Am. Chem. Soc. 1998, 120, 12849-12859.
21. (c) Hansen, T.; Daasbjerg, K.; Skrydstrup, T. Tetrahedron Lett. 2000, 41, 8645-8649.
22. Ogura, M.; Cordell, G. A.; Farnsworth, N. R. Phytochemistry 1978, 17, 957-961.
23. 2Ti(Cl)H, see: Sakai, S. J. Mol. Struct.: THEOCHEM 2001, 540, 157-169.
24. 1
25. 2O, the different results summarized in entries 1 and 2 of Table 1 might seem somewhat anomalous. To rationalize these results and the counterintuitive sequence given in Scheme 1, one of the referees suggested that water could act as a very good ligand for Ti that would increase the reduction potential and diminish the tendency toward β-elimination.
26. Ando, M.; Takase, K. Tetrahedron 1977, 33, 2785-2789.
27. 4b
28. (a) Bohlmann, F.; Ates, N.; Grenz, M. Phytochemistry 1982, 21, 1166-1168.
29. (b) Ahmed, A. A.; Abou-El-Ela, M.; Jakupovic, J.; Seif-El-Din, A. A.; Sabri, N. Phytochemistry 1990, 29, 3661-3663.
30. For the two-step original method, see: Grieco, P. A.; Nishizawa, M. J. Org. Chem. 1977, 42, 1717-1720.
31. (a) Doskotch, R. W.; El-Feraly, F. S. Can. J. Chem. 1969, 47, 1139-1142.
32. (b) Cardona, M. L.; Fernández, I.; B. García, J. R. Pedro, J. Nat. Prod. 1990, 53, 1042-1045.
33. Absolute configuration of 6 is known; see: Barrero, A. F.; Oltra, J. E.; Rodríguez-Gracía, I.; Barragán, A.; Alvarez, M. J. Nat. Prod. 2000, 63, 305-307.
34. Reported methods for transforming α-santonin (22) into other terpenoids might be advantageously applied to obtain eudesmanolides from 2, 11a, 17, and 19. For a review on chemical transformations of 22, see: Blay, G.; Cardona, L.; García, B.; Pedro, J. R. In Studies in Natural Products Chemistry; Atta-ur-Rahman, Ed.; Elsevier: Amsterdam, 2000; Vol. 24, pp 53-129.
35. Bermejo-Barrera, J.; Bretón, J. L.; Fajardo, M.; González, A. G. Tetrahedron Lett. 1967, 8, 3475-3476.
36. (a) Yamakawa, K.; Nishitani, K.; Tominaga, T. Tetrahedron Lett. 1975, 16, 2829-2832.
37. (b) Grieco, P. A.; Nishizawa, M. J. Chem. Soc., Chem. Commun. 1976, 582-583.
38. (c) Ando, M.; Wada, T.; Kusaka, H.; Takase, K.; Hirata, N.; Yanagi, Y. J. Org. Chem. 1987, 52, 4792-4796.