About the Chiral Stability of Germacrene B and the Biomimetic Synthesis of Guaiane Sesquiterpenes

Journal of Organic Chemistry

Volumn 62, Issue 21, 1997, Pages 7346-7350

  Minnaard, Adriaan J ^a   Wijnberg, Joannes B P A ^a   De Groot, Aede ^a  

^a WAGENINGEN UNIVERSITY   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000162171     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970902r     Document Type: Article

References (63)

1. For representative examples, see: (a) Allen, F. H.; Brown, E. D.; Rogers, D.; Sutherland, J. K. J. Chem. Soc., Chem. Commun. 1967, 1116. (b) Sutherland, J. K. Tetrahedron 1974, 30, 1651. (c) Brown, E. D.; Sam, T. W.; Sutherland, J. K.; Torre, A. J. Chem. Soc., Perkin Trans. 1 1975, 2326. (d) Brown, E. D.; Sutherland, J. K.; Sam, T. W. J. Chem. Soc., Perkin Trans. 1 1975, 2332. (e) Sam, T. W.; Sutherland, J. K. J. Chem. Soc., Perkin Trans. 1 1975, 2336.
2. For representative examples, see: (a) Allen, F. H.; Brown, E. D.; Rogers, D.; Sutherland, J. K. J. Chem. Soc., Chem. Commun. 1967, 1116. (b) Sutherland, J. K. Tetrahedron 1974, 30, 1651. (c) Brown, E. D.; Sam, T. W.; Sutherland, J. K.; Torre, A. J. Chem. Soc., Perkin Trans. 1 1975, 2326. (d) Brown, E. D.; Sutherland, J. K.; Sam, T. W. J. Chem. Soc., Perkin Trans. 1 1975, 2332. (e) Sam, T. W.; Sutherland, J. K. J. Chem. Soc., Perkin Trans. 1 1975, 2336.
3. For representative examples, see: (a) Allen, F. H.; Brown, E. D.; Rogers, D.; Sutherland, J. K. J. Chem. Soc., Chem. Commun. 1967, 1116. (b) Sutherland, J. K. Tetrahedron 1974, 30, 1651. (c) Brown, E. D.; Sam, T. W.; Sutherland, J. K.; Torre, A. J. Chem. Soc., Perkin Trans. 1 1975, 2326. (d) Brown, E. D.; Sutherland, J. K.; Sam, T. W. J. Chem. Soc., Perkin Trans. 1 1975, 2332. (e) Sam, T. W.; Sutherland, J. K. J. Chem. Soc., Perkin Trans. 1 1975, 2336.
4. For representative examples, see: (a) Allen, F. H.; Brown, E. D.; Rogers, D.; Sutherland, J. K. J. Chem. Soc., Chem. Commun. 1967, 1116. (b) Sutherland, J. K. Tetrahedron 1974, 30, 1651. (c) Brown, E. D.; Sam, T. W.; Sutherland, J. K.; Torre, A. J. Chem. Soc., Perkin Trans. 1 1975, 2326. (d) Brown, E. D.; Sutherland, J. K.; Sam, T. W. J. Chem. Soc., Perkin Trans. 1 1975, 2332. (e) Sam, T. W.; Sutherland, J. K. J. Chem. Soc., Perkin Trans. 1 1975, 2336.
5. For representative examples, see: (a) Allen, F. H.; Brown, E. D.; Rogers, D.; Sutherland, J. K. J. Chem. Soc., Chem. Commun. 1967, 1116. (b) Sutherland, J. K. Tetrahedron 1974, 30, 1651. (c) Brown, E. D.; Sam, T. W.; Sutherland, J. K.; Torre, A. J. Chem. Soc., Perkin Trans. 1 1975, 2326. (d) Brown, E. D.; Sutherland, J. K.; Sam, T. W. J. Chem. Soc., Perkin Trans. 1 1975, 2332. (e) Sam, T. W.; Sutherland, J. K. J. Chem. Soc., Perkin Trans. 1 1975, 2336.
6. The numbering system as given in structure 1 will be followed throughout the text of this paper.
7. In most naturally occurring ( E,E)-germacranes, C(14) and C(15) are Me groups. (E,E)-Germacranes in which C(14) or C(15) is oxidized are also frequently found in nature, see: Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman & Hall: London, 1991; Vol. 1, Mono- and Sesquiterpenoids.
8. During the rotation of a double bond, the vinylic hydrogen passes through the ring.
9. Wharton, P. S.; Poon, Y. C.; Kluender, H. C. J. Org. Chem. 1973, 38, 735.
10. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley Interscience: New York, 1994; pp 1166-1176.
11. Nishimura, K. Tetrahedron Lett. 1969, 3097.
12. Fransen, H. R.; Dormans, G. J. M.; Buck, H. M. Tetrahedron 1983, 39, 2981.
13. Watson, W. H.; Kashyap, R. P. J. Org. Chem. 1986, 51, 2521.
14. (a) Allen, F. H.; Rogers, D. J. Chem. Soc., Chem. Comm. 1967, 588.
15. (b) Allen, F. H.; Rogers, D. J. Chem. Soc. B 1971, 257.
16. Prefixes like S,S denote the chirality associated with the C(1)-C(10) and the C(4)-C(5) double bond, respectively, see: Cahn, R. S.; Ingold, C.; Prelog, V. Angew. Chem. 1966, 78, 413. For simplicity, C(7)-C(8) inversion is not considered.
17. Shirahama, H.; Osawa, E.; Matsumoto, T. Tetrahedron Lett. 1979, 2245.
18. Germacrone has been partly resolved by asymmetric reduction and back oxidation: Hill, R. K.; Fracheboud, M. G.; Sawada, S.; Carlson, R. M.; Van, S.-J. Tetrahedron Lett. 1978, 945.
19. Cane, D. E. Chem. Rev. 1990, 90, 1089.
20. See preceding paper.
21. Marshall et al. have used the same method in the synthesis of optically active betweenanenes and related (E)-cycloalkenes: (a) Marshall, J. A.; Audia, V. H. J. Org. Chem. 1987, 52, 1106. (b) Marshall, J. A.; Audia, V. H.; Jenson, T. M.; Guida, W. C. Tetrahedron 1986, 42, 1703 and references cited therein.
22. Marshall et al. have used the same method in the synthesis of optically active betweenanenes and related (E)-cycloalkenes: (a) Marshall, J. A.; Audia, V. H. J. Org. Chem. 1987, 52, 1106. (b) Marshall, J. A.; Audia, V. H.; Jenson, T. M.; Guida, W. C. Tetrahedron 1986, 42, 1703 and references cited therein.
23. It was assumed that replacement of a Me(15) hydrogen atom by a hydroxyl group would have no effect on the conformational behavior.
24. It is obvious that this ee will depend on the racemization rate of 2.
25. 3 stands for europium tris[3-(heptafluoropropylhydroxyrnethylene)-(+)-camphorate].
26. The transannular cyclization of (E,E)-germacrane 4,5-epoxides constitutes an important step in the biosynthesis of cis-fused guaianes, see: Fischer, N. H. In Recent Advances in Phytochemistry, Vol. 24: Biochemistry of the Mevalonic Acid Pathway to Terpenoids; Towers, G. H. N., Stafford, H. A., Eds.; Plenum Press: New York, 1990; Chapter 4.
27. Marco, J. A.; Sanz-Cervera, J. F.; García-Lliso, V.; Domingo, L. R.; Carda, M.; Rodríguez, S.; López-Ortiz, F.; Lex, J. Liebigs Ann. Chem. 1995, 1837 and references cited therein.
28. Cyclization of geometric isomers of simple (E,E)-germacranes have been performed, inter alia, see: (a) Kodama, M.; Yokoo, S.; Matsuki, Y.; Itô, S. Tetrahedron Lett. 1979, 1687 and references cited therein, (b) Williams, J. R.; Callahan, J. F.; Blount, J. F. J. Org. Chem. 1981, 46, 2665.
29. Cyclization of geometric isomers of simple (E,E)-germacranes have been performed, inter alia, see: (a) Kodama, M.; Yokoo, S.; Matsuki, Y.; Itô, S. Tetrahedron Lett. 1979, 1687 and references cited therein, (b) Williams, J. R.; Callahan, J. F.; Blount, J. F. J. Org. Chem. 1981, 46, 2665.
30. (a) Toma, K.; Murae, T.; Takahashi, T. Chem. Lett. 1982, 551.
31. (b) De Pascual Teresa, J.; González, M. S.; Caballero, M. C.; Parra, T.; Bellido, I. S. Tetrahedron Lett. 1987, 28, 821.
32. (c) González, A. G.; Galindo, A.; Afonso, M. M.; Mansilla, H.; López, M. Tetrahedron 1988, 44, 4585.
33. (d) Delgado, G.; Guzmán, S. J. Chem. Soc., Chem. Commun. 1992, 606.
34. In the NMR spectra of 1, similar effects were observed.
35. Siever, R. E.; Kime, K. A. Aldrichimica Acta 1977, 10, 54.
36. A similar reasoning has been made for the biological epoxidation of (E,E)-germacranes, see: Fischer, N. H. Rev. Latinoamer. Quím. 1978, 9, 41.
37. (a) Johnson, R. A.; Sharpless, K. B. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; Chapter 4.
38. (b) Katsuki, T.; Martin, V. S. Org. React. 1996, 48, 1.
39. 2 was the carrier gas. Peaks were partly resolved and integrated manually.
40. In different runs the optical rotation did not exceed 5°.
41. With (+)-DET as the chiral ligand, (R,R)-2 remains largely unoxidized, see ref 27a, pp 104-108.
42. Kuroyanagi, M.; Ueno, A.; Koyoma, K.; Natori, S. Chem. Pharm. Bull. 1990, 38, 55.
43. Herz, W. In Chemistry in Botanical Classification. Nobel Symposium 25; Bendz, G., Santesson, T., Eds.; Academic Press: New York, 1973; pp 153-172.
44. (a) Bohlmann, F.; Borthakur, N.; Jakupovic, J.; Pickard, J. Phytochemistry 1982, 21, 1357.
45. (b) Barrero, A. F.; Sánchez, J. F.; Molina, J.; Barrón, A.; Del Mar Salas, M. Phytochemistry 1990, 29, 3575.
46. The possible role of melampolides in guaiane biosynthesis is currently studied at our department. To be published.
47. Chiral GC could not be used to establish the ee of 5 because of its thermal instability.
48. Because only a single peak was observed, the ee of 6 could not be determined with chiral GC. In this respect, it should be noted that the enantioselectivity of the Sharpless epoxidation of allylic alcohols almost invariably approaches 100%. See reference 27a, p 104.
49. 1H NMR spectrum of the crude product mixture.
50. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, Plenum Press: New York, 1990; part A, p 314.
51. (a) Bohlmann, F.; Jakupovic, J. Phytochemistry 1979, 18, 131.
52. (b) Yu, S.; Fang, N.; Mabry, T. J.; Abboud, K. A.; Simonsen, S. H. Phytochemistry 1988, 27, 2887.
53. (c) Zdero, C.; Bohlmann, F.; King, R. M. Phytochemistry 1990, 29, 3201.
54. (d) Gao, F.; Wang, H.; Mabry, T. J. Watson, W. H.; Kashyap, R. P. Phytochemistry 1990, 29, 551.
55. (e) Gao F.; Wang, H.; Mabry, T. J. Phytochemistry 1990, 29, 1601.
56. (a) Fischer, N. H.; Wiley, R. A.; Perry, D. L. Rev. Latinoamer. Quím, 1976, 7, 87.
57. (b) Herz, W. Israel J. Chem. 1977, 16, 32.
58. The biotransformation of racemic germacrone to enantiomerically enriched germacrone-4,5-epoxide by plant cell cultures has been reported, see: (a) Hikino, H.; Konno, C.; Nagashima, T.; Kohama, T.; Takemoto, T.; Chem. Pharm. Bull. 1977, 25, 6. (b) Sakui, N.; Kuroyanagi, M.; Ishitobi, Y.; Ueno, A. Phytochemistry 1992, 31, 143. (c) Sakamoto, S.; Tsuchiya, N.; Kuroyanagi, M.; Ueno, A. Phytochemistry 1994, 55, 1215.
59. The biotransformation of racemic germacrone to enantiomerically enriched germacrone-4,5-epoxide by plant cell cultures has been reported, see: (a) Hikino, H.; Konno, C.; Nagashima, T.; Kohama, T.; Takemoto, T.; Chem. Pharm. Bull. 1977, 25, 6. (b) Sakui, N.; Kuroyanagi, M.; Ishitobi, Y.; Ueno, A. Phytochemistry 1992, 31, 143. (c) Sakamoto, S.; Tsuchiya, N.; Kuroyanagi, M.; Ueno, A. Phytochemistry 1994, 55, 1215.
60. The biotransformation of racemic germacrone to enantiomerically enriched germacrone-4,5-epoxide by plant cell cultures has been reported, see: (a) Hikino, H.; Konno, C.; Nagashima, T.; Kohama, T.; Takemoto, T.; Chem. Pharm. Bull. 1977, 25, 6. (b) Sakui, N.; Kuroyanagi, M.; Ishitobi, Y.; Ueno, A. Phytochemistry 1992, 31, 143. (c) Sakamoto, S.; Tsuchiya, N.; Kuroyanagi, M.; Ueno, A. Phytochemistry 1994, 55, 1215.
61. For a general description of the experimental procedures employed in this research, see: Minnaard, A. J.; Wijnberg, J. B. P. A.; de Groot, A. Tetrahedron 1994, 50, 4755.
62. 5N.
63. 1H NMR spectrum of 7 revealed the presence of a small amount of 8.