Concise total syntheses of palominol, dolabellatrienone, β-araneosene, and isoedunol via an enantioselective Diels-Alder macrobicyclization

Journal of the American Chemical Society

Volumn 128, Issue 3, 2006, Pages 740-742

  Snyder, Scott A ^a   Corey, E J ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BETA ARANEOSENE; DOLABELLATRIENONE; ISOEDUNOL; MACROCYCLIC COMPOUND; PALOMINOL; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CYCLIZATION; DIELS ALDER REACTION; ENANTIOSELECTIVITY; HYDROGEN BOND; PHOTOCHEMISTRY; QUANTUM YIELD; REACTION ANALYSIS; REDUCTION; SYNTHESIS; WOLFF KISHNER REDUCTION; X RAY CRYSTALLOGRAPHY;

BENZOPYRANS; CYCLIZATION; DITERPENES; STEREOISOMERISM;

EID: 31444431583     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0576379     Document Type: Article

References (42)

1. For reviews, see: (a) Corey, E. J. Angew. Chem., Int. Ed. 2002, 41, 1650.
2. (b) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vasillikogiannakis, G. E. Angew. Chem., Int. Ed. 2002, 41, 1668.
3. For other approaches from our group, see: (a) Kingsbury, J. S.; Corey, E. J. J. Am. Chem. Soc. 2005, 127, 13813.
4. (b) Hu, T.; Corey, E. J. Org. Lett. 2002, 4, 2441.
5. (c) Corey, E. J.; Kania, R. S. Tetrahedron Lett. 1998, 39, 741.
6. (d) Corey, E. J.; Kania, R. S. J. Am. Chem. Soc. 1996, 118, 1229.
7. For a review, see: Rodríguez, A. D.; González, E.; Ramírez, C. Tetrahedron 1998, 54, 11683.
8. Isolation: (a) Shin, J.; Fenical, W. J. Org. Chem. 1991, 56, 3392.
9. (b) Jenny, L.; Borschberg, H.-J. Helv. Chim. Acta 1995, 78, 715.
10. Total syntheses: (c) See ref 2a.
11. Isolation: (a) See ref 4a.
12. Total syntheses: (b) See ref 2c.
13. (c) See ref 2d.
14. (d) Miyaoka, H.; Isaji, Y.; Mitome, H.; Yamada, Y. Tetrahedron 2003, 59, 61.
15. Isolation: (a) Look, S. A.; Fenical, W. J. Org. Chem. 1982, 47, 4129.
16. (b) Rodrguez, A. D.; Acosta, A. L.; Dhasmana, H. J. Nat. Prod. 1993, 56, 1843.
17. Total syntheses: (c) See ref 2c.
18. (d) See ref 5d.
19. (a) Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808.
20. (b) Ryu, D. H.; Lee, T. W.; Corey, E. J. J. Am. Chem. Soc. 2002, 124, 9992.
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22. (d) Ryu, D. H.; Zhou, G.; Corey, E. J. J. Am. Chem. Soc. 2004, 126, 4800.
23. (e) Hu, Q.-Y.; Zhou, G.; Corey, E. J. J. Am. Chem. Soc. 2004, 126, 13708.
24. For selected examples of enantioselective, intramolecular Diels-Alder reactions, see: (f) Zhou, G.; Hu, Q.-Y.; Corey, E. J. Org. Lett. 2003, 5, 3979.
25. (g) Wilson, R. M.; Jen, W. S.; MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 11616.
26. See Supporting Information for the preparation of this compound.
27. See ref 2d for the synthesis of this fragment.
28. Vanderwal, C. D.; Vosburg, D. A.; Weiler, S.; Sorensen, E. J. J. Am. Chem. Soc. 2003, 125, 5393.
29. Previous studies in these laboratories indicated that related farnesyl couplings using several different palladium sources and reaction conditions afforded only isomeric mixtures. See: Kania, R. S. Ph.D. Thesis, Harvard University, 1997.
30. See Supporting Information for further details on the optimization of this step and the determination of the absolute configuration of 12.
31. Corey, E. J.; Beames, D. J. J. Am. Chem. Soc. 1973, 95, 5829.
32. For an excellent review on the formation of cyclopentyl rings via ring contraction reactions of six-membered carbocycles, see: Silva, L. F. Tetrahedron 2002, 58, 9137.
33. The use of other solvents, reaction temperatures, and untreated Raney Ni in the desulfurization step caused olefinic reduction.
34. For reviews, see: (a) Kirmse, W. Eur. J. Org. Chem. 2002, 2193.
35. (b) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; John Wiley & Sons: New York, 1998; p 652.
36. (a) Nicolaou, K. C.; Montagnon, T.; Baran, P. S. Angew. Chem., Int. Ed. 2002, 41, 993.
37. (b) Nicolaou, K. C.; Gray, D. L. F.; Montagnon, T.; Harrison, S. T. Angew. Chem., Int. Ed. 2002, 41, 996. All other protocols, such as Saegusa oxidation, provided markedly inferior yields.
38. Lombardo, L.; Mander, L. N. Synthesis 1980, 368.
39. 2 at 25 °C (Smith, N. B.; Derrien, N.; Lloyd, M. C.; Taylor, S. J. C.; Chaplin, D. A.; McCague, R. Tetrahedron Lett. 2001, 42, 1347) afforded only recovered the β,γ-unsaturated isomer of 15, while exposure to DBU/toluene (1:1) at 110 °C effected only partial conversion to 15 after 18 h of reaction time.
40. The only side product in this conversion is that bearing a tetrasubstituted olefin adjoining the A and B rings; such a side product has been formed from 28 before through a thermal reaction: Fuchs, B.; Loewenthal, H. J. E. Tetrahedron 1960, 11, 199.
41. Corey, E. J.; Ensley, H. E. J. Am. Chem. Soc. 1975, 97, 6908.
42. The selectivity in this event appears to be unique, as related model compounds derived from 5α-cholestan-3-one afforded products corresponding to β-araneosene (1). We ascribe the unique reactivity to destabilizing steric interactions between the isopropylidene methyl groups and the adjoining 11-membered ring that are relieved upon tertiary radical formation followed by rapid H-atom abstraction from THF. Use of the proton source tert-butyl alcohol afforded a 1:1 mixture of 29 and β-araneosene (1).