Total synthesis of the enantiomer of the furanocembrane rubifolide

Journal of Organic Chemistry

Volumn 62, Issue 13, 1997, Pages 4313-4320

  Marshall, James A ^a   Sehon, Clark A ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FURAN DERIVATIVE; RUBIFOLIDE; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; ENANTIOMER; MARINE ENVIRONMENT; OXIDATION; SYNTHESIS;

EID: 0030796165     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970360d     Document Type: Article

References (26)

1. Marshall, J. A.; DuBay, W. J. J. Org. Chem. 1993, 58, 574.
2. For a review, see: Paquette, L. A. Chemtracts: Org. Chem. 1992, 5, 141. The only other synthesis of a furanocembrane completed to date is that of racemic acerosolide. Paquette, L. A.; Astles, P. C. J. Org. Chem. 1993, 58, 165.
3. For a review, see: Paquette, L. A. Chemtracts: Org. Chem. 1992, 5, 141. The only other synthesis of a furanocembrane completed to date is that of racemic acerosolide. Paquette, L. A.; Astles, P. C. J. Org. Chem. 1993, 58, 165.
4. Marshall, J. A.; DuBay, W. J. J. Org. Chem. 1994, 59, 1703.
5. Williams, D.; Andersen, R. J.; VanDuyne, G. D.; Clardy, J. J. Org. Chem. 1987, 52, 332.
6. Current prices for (R)- and (S)-perillyl alcohol from the 1995-96 Aldrich Chemical Catalog are $27.60/g and $1.36/g.
7. Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 3769.
8. This aldehyde was prepared as follows: chemical equation presented. For details see the Supporting Information.
9. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P. Masamune, S.; Roush, W. R. Tetrahedron Lett. 1984, 2183.
10. Marshail, J. A.; Sehon, C. A. J. Org. Chem. 1995, 60, 5966.
11. Marshall, J. A.; Wolf, M. A. J. Org. Chem. 1996, 61, 3238.
12. Singaram, B.; Fisher, G. B.; Fuller, J. C.; Harrison, J.; Alvarez, S. G.; Burkhardt, E. R.; Goralski, C. T. J. Org. Chem. 1994, 59, 6378.
13. 13 Thus the failure of the latter to cyclize is most likely the result of energy differences in the transition states. Calculations of these differences are, at present, beyond our capabilities. The calculated ground state conformation of the allenic acid 21 differed markedly from that of 1 and 16. Significantly, the allylic OH of the latter two was favorably disposed to interact with the alkynyl moiety, whereas in 21 that OH was oriented away from the alkyne.
14. The program Macromodel 4.5 was employed for these calculations. Global minimum multiple conformer searching was achieved with the Monte Carlo subroutine in BATCHMIN through multiple step interactions (typically 1000) until the minimum energy conformer was found multiple times (10 or more). For a description of the program, see: (a) Mohamadi, F.; Richards, N. G.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. (b) Chang, G.; Guida, W. C.; Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379.
15. The program Macromodel 4.5 was employed for these calculations. Global minimum multiple conformer searching was achieved with the Monte Carlo subroutine in BATCHMIN through multiple step interactions (typically 1000) until the minimum energy conformer was found multiple times (10 or more). For a description of the program, see: (a) Mohamadi, F.; Richards, N. G.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440. (b) Chang, G.; Guida, W. C.; Still, W. C. J. Am. Chem. Soc. 1989, 111, 4379.
16. Marshall, J. A.; Wang, X.-j. J. Org. Chem. 1992, 57, 3387.
17. Gilbert, S. C.; Weerasooriya, U. J. Org. Chem. 1979, 44, 4997.
18. Narasaka, K.; Morikawa, A.; Saigo, K.; Mukaiyama, T. Bull. Soc. Chem. Jpn. 1977, 50, 2773.
19. Cf. Marshall, J. A.; Bennett, C. E. J. Org. Chem. 1994, 59, 6110.
20. Mandai, T.; Tsuji, J.; Tsujiguchi, Y. J. Am. Chem. Soc. 1993, 115, 5865.
21. Marshall, J. A.; Bartley, G. S.; Wallace E. M. J. Org. Chem. 1996, 61, 5729.
22. 13
23. Trost, B. M.; Belletire, J. L.; Godleski, S.; McDougal, P. G.; Balkovec, J. M.; Baldwin, J. J.; Christy, E.; Ponticello, G. S.; Varga, S. L.; Springer, J. D. J. Org. Chem. 1986, 51, 2370.
24. This analysis was performed by Dr. Michael Sabat of this department.
25. Copies of the spectra were kindly provided by Professor R. J. Andersen (University of British Columbia).
26. Dess, D. B.; Martin, J. C. J. Org. Chem. 1983, 48, 4156.