A total synthesis of (±)-trans-kumausyne

Organic Letters

Volumn 7, Issue 16, 2005, Pages 3493-3495

  Chandler, Carley L ^a   Phillips, Andrew J ^a  

^a UNIVERSITY OF COLORADO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FURAN DERIVATIVE; KUMAUSYNE;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; LAURENCIA; STEREOISOMERISM; SYNTHESIS;

CYCLIZATION; FURANS; LAURENCIA; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 23944513776     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol051199t     Document Type: Article

References (33)

1. (a) Suzuki, T.; Koizumi, K.; Suzuki, M.; Kurosawa, E. Chem. Lett. 1983, 1643.
2. (b) Suzuki, T.; Koizumi, K.; Suzuki, M.; Kurosawa, E. Chem. Lett. 1983, 1639.
3. (a) Fukuzawa, A.; Kurosawa, E.; Irie, T. Tetrahedron Lett. 1972, 13, 3.
4. (b) Furusaki, A.; Kurosawa, E.; Fukuzawa, A.; Irie, T. Tetrahedron Lett. 1973, 14, 4579.
5. Total syntheses: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378.
6. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789.
7. (c) Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 63, 916.
8. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7757.
9. Total syntheses: (a) Grese, T. A. Hutchinson, K. D.; Overman, L. E. J. Org. Chem. 1993, 58, 2468.
10. (b) Evans, P. A.; Murthy, V. S.; Roseman, J. D.; Rheingold, A. L. Angew. Chem., Int. Ed. 1999, 38, 3175.
11. (a) Fernandez De La Pradilla, R.; Viso, A. Rec. Res. Dev. Org. Bioorg. Chem. 2001, 4, 123.
12. (b) Gadikota, R. R.; Callam, C. S.; Lowary, T. L. J. Org. Chem. 2001, 66, 9046.
13. (c) Garcia, C.; Martin, T.; Martin, V. S. J. Org. Chem. 2001, 66, 1420.
14. (d) Mereyala, H. B.; Gadikota, R. Tetrahedron: Asymmetry 2000, 11, 743.
15. (e) Fernandez de la Pradilla, R.; Montero, C.; Priego, J.; Martinez-Cruz, L. A. J. Org. Chem. 1998, 63, 9612.
16. (f) Andrey, O.; Glanzmann, C.; Landais, Y.; Parra-Rapado, L. Tetrahedron 1997, 53, 2835.
17. (g) Lee, E.; Yoo, S.-K.; Choo, H.; Song, H. Y Tetrahedron Lett. 1998, 39, 317.
18. (a) Minger, T. L.; Phillips, A. J. Tetrahedron Lett. 2002, 43, 5357.
19. (b) Pfeiffer, M. W. B.; Phillips, A. J. J. Am. Chem. Soc. 2005, 127, 5334.
20. (a) Kotsuki, H.; Asao, K.; Ohnishi, H. Bull. Chem. Soc. Jpn. 1984, 57, 3339.
21. (b) For a catalytic asymmetric synthesis, see: Evans, D. A.; Barnes, D. M.; Johnson, J. S.; Lectka, T.; von Matt, P.; Miller, S. J.; Murry, J. A.; Norcross, R. D.; Shaughnessy, E. A.; Campos, K. R. J. Am. Chem. Soc. 1999, 121, 7582.
22. For other examples of tandem ROM-RCM in a target-oriented setting, see: (a) Blechert, S.; Stapper, C. Eur. J. Org. Chem. 2002, 16, 2855.
23. (b) Stapper, C.; Blechert, S. J. Org. Chem. 2002, 67, 6456.
24. (c) Stragies, R.; Blechert, S. J. Am. Chem. Soc. 2000, 122, 9584.
25. (d) Wrobleski, A.; Sahasrabudhe, K.; Aube, J. J. Am. Chem. Soc. 2002, 124, 9974.
26. This sequence could also be carried out without purification of sensitive enone 2. The overall yield for the sequence from 1→3 by this permutation was 49%.
27. (a) Mahoney, W. S.; Brestensky, D. M.; Stryker, J. M. J. Am. Chem. Soc. 1988, 110, 291.
28. (b) Lipshutz, B. H.; Keith, J.; Papa, P.; Vivian, R. Tetrahedron Lett. 1998, 39, 4627.
29. Kotsuki, H.; Arimura, K.; Araki, T.; Shinohara, T. Synlett 1999, 462.
30. Efforts to perform the Baeyer-Villiger oxidation at later points in the sequence were unsuccessful due to competitive olefin epoxidation. Epoxidation with MCPBA alone produced mixtures of products derived from epoxidation and Baeyer-Villiger oxidation.
31. In all other syntheses of kumausyne and kumausallene, the pentenyl side chain was installed by a variation on Overman's original solution (see ref 3a), which consists of Sakurai allylation of a related aldehyde with 3-trimethylsilyl-1-pentene or 3-triethylsilyl-1-pentene. Although these reagents are prepared in a straightforward manner by the scheme shown below, they are low-boiling and difficult to handle. The protocol described here has the advantage of employing commercially available materials and should, in principle, be quite general provided that the alkene required for the subsequent cross-metathesis is readily available.
32. (a) Nicholas, K. M.; Pettit, R. J. Organomet. Chem. 1972, 44, C21.
33. (b) For a closely related example, see: Overman, L. E.; Berger, D.; Renhowe, P. A. J. Am. Chem. Soc. 1993, 115, 9305.