Highly improved synthesis of (+)-aureol via (-)-neoavarone and (-)-neoavarol, by employing salcomine oxidation and acid-induced rearrangement/cyclization strategy

Synlett

Volumn , Issue 3, 2003, Pages 329-332

  Suzuki, Akiyuki ^b   Nakatani, Mari ^a   Nakamura, Masahiko ^c   Kawaguchi, Keiko ^b   Inoue, Munenori ^a   Katoh, Tadashi ^a,c  

^a SAGAMI CHEMICAL RESEARCH CENTER   (Japan)

^b KITASATO UNIVERSITY   (Japan)

^c TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Aureol; Marine natural product; Neoavarol; Neoavarone; Rearrangement cyclization reaction

Indexed keywords

ACID; ALCOHOL DERIVATIVE; AMINE; AVAROL; AVARONE; KETONE DERIVATIVE; NATURAL PRODUCT; PHENOL DERIVATIVE;

ARTICLE; BIOMIMETICS; CARBON NUCLEAR MAGNETIC RESONANCE; CYCLIZATION; DRUG SYNTHESIS; INFRARED SPECTROSCOPY; MASS SPECTROMETRY; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0037288255     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-37130     Document Type: Article

References (36)

1. For recent excellent reports on the clerodane diterpenoids and related compounds including marine natural products, see: (a) Faulkner, D. J. Nat. Prod. Rep. 2002, 19, 1. (b) Capon, R. J. Eur. J. Org. Chem. 2001, 633. (c) Tokoroyama, T. Synthesis 2000, 611. (d) Capon, R. J. In Studies in Natural Products Chemistry, Vol. 15. Atta-ur-Rahman, Ed.; Elsevier Science B.V.: Amsterdam, 1995, 289-326.
2. For recent excellent reports on the clerodane diterpenoids and related compounds including marine natural products, see: (a) Faulkner, D. J. Nat. Prod. Rep. 2002, 19, 1. (b) Capon, R. J. Eur. J. Org. Chem. 2001, 633. (c) Tokoroyama, T. Synthesis 2000, 611. (d) Capon, R. J. In Studies in Natural Products Chemistry, Vol. 15: Atta-ur-Rahman, Ed.; Elsevier Science B.V.: Amsterdam, 1995, 289-326.
3. For recent excellent reports on the clerodane diterpenoids and related compounds including marine natural products, see: (a) Faulkner, D. J. Nat. Prod. Rep. 2002, 19, 1. (b) Capon, R. J. Eur. J. Org. Chem. 2001, 633. (c) Tokoroyama, T. Synthesis 2000, 611. (d) Capon, R. J. In Studies in Natural Products Chemistry, Vol. 15: Atta-ur-Rahman, Ed.; Elsevier Science B.V.: Amsterdam, 1995, 289-326.
4. For recent excellent reports on the clerodane diterpenoids and related compounds including marine natural products, see: (a) Faulkner, D. J. Nat. Prod. Rep. 2002, 19, 1. (b) Capon, R. J. Eur. J. Org. Chem. 2001, 633. (c) Tokoroyama, T. Synthesis 2000, 611. (d) Capon, R. J. In Studies in Natural Products Chemistry, Vol. 15; Atta-ur-Rahman, Ed.; Elsevier Science B.V.: Amsterdam, 1995, 289-326.
5. Djura, P.; Stierle, D. B.; Sullivan, B.; Faulkner, D. J.; Arnold, E.; Clardy, J. J. Org. Chem. 1980, 45, 1435.
6. Ciminiello, P.; Dell' Aversano, C.; Fattorusso, E.; Magno, S.; Pansini, M. J. Nat. Prod. 2000, 63, 263. Longley, R. E.; McConnell, O. J.; Essich, E.; Harmody, D. J. Nat. Prod. 1993, 56, 915.
7. Longley, R. E.; McConnell, O. J.; Essich, E.; Harmody, D. J. Nat. Prod. 1993, 56, 915.
8. Wright, A. E.; Cross, S. S.; Burres, N. S.; Koehn, F. Harbor Branch Oceanographics Institution Inc. PCT WO 9112250A1, August 22, 1991.
9. Nakamura, M.; Suzuki, A.; Nakatani, M.; Fuchikami, T.; Inoue, M.; Katoh, T. Tetrahedron Lett. 2002, 43, 6929.
10. Kawano, H.; Itoh, M.; Katoh, T.; Terashima, S. Tetrahedron Lett. 1997, 38, 7769.
11. Hagiwara, H.; Uda, H. J. Org. Chem. 1988, 53, 2308.
12. Iguchi, K.; Sahashi, A.; Kohno, J.; Yamada, Y. Chem. Pharm. Bull. 1990, 38, 1121.
13. The total synthesis of avarone (i)and avarol (ii, Figure 2), which correspond to the C4 endo-olefinic isomers of neoavarone(10) and neoavarol(11), respectively, have been previously achieved by several research groups, see: (a) Ling, T.; Poupon, E.; Rueden, E. J.; Kim, S. H.; Theodorakis, E. A. J. Am. Chem. Soc. 2002, 124, 12261. (b) Ling, T.; Xiang, A. X.; Theodorakis, E. A. Angew. Chem. Int. Ed. 1999, 38, 3089. (c) Locke, E. P.; Hecht, S. M. Chem. Commun. 1996, 2717. (d) An, J.; Wiemer, D. F. J. Org. Chem. 1996, 61, 8775. (e) Sarma, A. S.; Chattopadhyay, P. J. Org. Chem. 1982, 47, 1727.
14. The total synthesis of avarone (i)and avarol (ii, Figure 2), which correspond to the C4 endo-olefinic isomers of neoavarone(10) and neoavarol(11), respectively, have been previously achieved by several research groups, see: (a) Ling, T.; Poupon, E.; Rueden, E. J.; Kim, S. H.; Theodorakis, E. A. J. Am. Chem. Soc. 2002, 124, 12261. (b) Ling, T.; Xiang, A. X.; Theodorakis, E. A. Angew. Chem. Int. Ed. 1999, 38, 3089. (c) Locke, E. P.; Hecht, S. M. Chem. Commun. 1996, 2717. (d) An, J.; Wiemer, D. F. J. Org. Chem. 1996, 61, 8775. (e) Sarma, A. S.; Chattopadhyay, P. J. Org. Chem. 1982, 47, 1727.
15. The total synthesis of avarone (i)and avarol (ii, Figure 2), which correspond to the C4 endo-olefinic isomers of neoavarone(10) and neoavarol(11), respectively, have been previously achieved by several research groups, see: (a) Ling, T.; Poupon, E.; Rueden, E. J.; Kim, S. H.; Theodorakis, E. A. J. Am. Chem. Soc. 2002, 124, 12261. (b) Ling, T.; Xiang, A. X.; Theodorakis, E. A. Angew. Chem. Int. Ed. 1999, 38, 3089. (c) Locke, E. P.; Hecht, S. M. Chem. Commun. 1996, 2717. (d) An, J.; Wiemer, D. F. J. Org. Chem. 1996, 61, 8775. (e) Sarma, A. S.; Chattopadhyay, P. J. Org. Chem. 1982, 47, 1727.
16. The total synthesis of avarone (i)and avarol (ii, Figure 2), which correspond to the C4 endo-olefinic isomers of neoavarone(10) and neoavarol(11), respectively, have been previously achieved by several research groups, see: (a) Ling, T.; Poupon, E.; Rueden, E. J.; Kim, S. H.; Theodorakis, E. A. J. Am. Chem. Soc. 2002, 124, 12261. (b) Ling, T.; Xiang, A. X.; Theodorakis, E. A. Angew. Chem. Int. Ed. 1999, 38, 3089. (c) Locke, E. P.; Hecht, S. M. Chem. Commun. 1996, 2717. (d) An, J.; Wiemer, D. F. J. Org. Chem. 1996, 61, 8775. (e) Sarma, A. S.; Chattopadhyay, P. J. Org. Chem. 1982, 47, 1727.
17. The total synthesis of avarone (i)and avarol (ii, Figure 2), which correspond to the C4 endo-olefinic isomers of neoavarone(10) and neoavarol(11), respectively, have been previously achieved by several research groups, see: (a) Ling, T.; Poupon, E.; Rueden, E. J.; Kim, S. H.; Theodorakis, E. A. J. Am. Chem. Soc. 2002, 124, 12261. (b) Ling, T.; Xiang, A. X.; Theodorakis, E. A. Angew. Chem. Int. Ed. 1999, 38, 3089. (c) Locke, E. P.; Hecht, S. M. Chem. Commun. 1996, 2717. (d) An, J.; Wiemer, D. F. J. Org. Chem. 1996, 61, 8775. (e) Sarma, A. S.; Chattopadhyay, P. J. Org. Chem. 1982, 47, 1727.
18. The starting material 8 was prepared from (+)-Wieland-Miescher ketone analogue 7 (>99% ee) according to the following Scheme 4. For further details, see: Nakatani, M.; Nakamura, M.; Suzuki, A.; Inoue, M.; Katoh, T. Org. Lett. 2002, 4, 4483.
19. (a) Taishi, T.; Takechi, S.; Mori, S. Tetrahedron Lett. 1998, 39, 4347.
20. (b) Aristoff, P. A.; Harrison, A. W.; Huber, A. M. Tetrahedron Lett. 1984, 25, 3955.
21. (c) Welch, S. C.; Pao, A. S. C. P. Tetrahedron Lett. 1977, 505.
22. (d) Feutrill, G. I.; Mirrington, R. N. Aust. J. Chem. 1972, 25, 1719.
23. (e) Bartlett, P. A.; Johnson, W. S. Tetrahedron Lett. 1970, 4459.
24. 30O: C, 84.51; H, 10.13. Found: C, 84.63; H, 10.33.
25. (a) Katoh, T.; Nakatani, M.; Shikita, S.; Sampe, R.; Ishiwata, A.; Ohmori, O.; Nakamura, M.; Terashima, S. Org. Lett. 2001, 3, 2701.
26. (b) Miyata, F.; Yoshida, S.; Yamori, T.; Katoh, T. Heterocycles 2001, 54, 619.
27. (c) Saito, N.; Obara, Y.; Aihara, T.; Harada, S.; Shida, Y.; Kubo, A. Tetrahedron 1994, 50, 3915.
28. (d) Yoshida, K.; Nakajima, S.; Ohnuma, T.; Ban, Y.; Shibasaki, M.; Aoe, K.; Date, T. J. Org. Chem. 1988, 53, 5355.
29. (e) Wakamatsu, T.; Nishi, T.; Ohnuma, T.; Ban, Y. Synth. Commun. 1984, 14, 1167.
30. +]: 313.2167. Found: 313.2195.
31. 10c,10d. For additional examples, see: (a) Kawai, N.; Fujibayashi, Y.; Kuwabara, S.; Takao, K.; Ijuin, Y.; Kobayashi, S. Tetrahedron 2000, 56, 6467. (b) Watson, A. T.; Park, K.; Wiemer, D. F. J. Org. Chem. 1995, 60, 5102. (c) Harada, N.; Sugioka, T.; Ando, Y.; Uda, H.; Kuriki, T. J. Am. Chem. Soc. 1988, 110, 8483.
32. 10c,10d. For additional examples, see: (a) Kawai, N.; Fujibayashi, Y.; Kuwabara, S.; Takao, K.; Ijuin, Y.; Kobayashi, S. Tetrahedron 2000, 56, 6467. (b) Watson, A. T.; Park, K.; Wiemer, D. F. J. Org. Chem. 1995, 60, 5102. (c) Harada, N.; Sugioka, T.; Ando, Y.; Uda, H.; Kuriki, T. J. Am. Chem. Soc. 1988, 110, 8483.
33. 10c,10d. For additional examples, see: (a) Kawai, N.; Fujibayashi, Y.; Kuwabara, S.; Takao, K.; Ijuin, Y.; Kobayashi, S. Tetrahedron 2000, 56, 6467. (b) Watson, A. T.; Park, K.; Wiemer, D. F. J. Org. Chem. 1995, 60, 5102. (c) Harada, N.; Sugioka, T.; Ando, Y.; Uda, H.; Kuriki, T. J. Am. Chem. Soc. 1988, 110, 8483.
34. +]: 315.2324. Found: 315.2344.
35. +): 314.2246. Found: 314.2241.
36. 6 the cis-fused decalin system 6 [(+)-arenarol] was used as the substrate for the key acid-induced rearrangement/cyclization reaction, while in the present study the trans-fused decalin system 11 [(-)-neoavarol] is employed instead of 6. In these rearrangement/cyclization process, we believe that the same carbocation intermediate such as II would be generated in situ from 6 and 11, respectively, leading ultimately to the formation of (+)-aureol (1). And furthermore, we have already reported a similar carbocation-mediated domino process that is initiated by Lewis acid-induced epoxide-opening, followed by consecutive suprafacial methanide and hydride migrations. For further details, see the literature cited in ref. 11.