A Total Synthesis of the Racemic Sesquiterpene Parvifoline

Journal of Organic Chemistry

Volumn 63, Issue 9, 1998, Pages 2918-2921

  Covarrubias Zúñiga, Adrián ^a   Cantú, Fernando ^a   Maldonado, Luis A ^a  

^a Instituto de Quimica de la UNAM   (Mexico)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542396133     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972092p     Document Type: Article

References (29)

1. (1)(a) Bohlmann, F.; Zdero, Ch. Chem. Ber. 1977, 110, 468.
2. (b) Joseph-Nathan, P.; Hernández, J. D.; Román, L. U.; García, E.; Mendoza, V. Phytochemistry 1982, 21, 669.
3. (c) Joseph-Nathan, P.; Hernández, J. D.; Román, L. U.; García, E.; Mendoza, V.; Mendoza, S. Phytochemistry 1982, 21, 1129.
4. (d) García, E.; Mendoza, V.; Guzmán, J. A. J. Nat. Prod. 1988, 51, 150.
5. (a) García, E.; Mendoza, V.; Guzmán, J. A. J. Nat. Prod. 1987, 50, 1055.
6. (b) Joseph-Nathan, P.; Hernández-Medel, M. del R.; Martínez, E.; Rojas-Gardida, M.; Cerda, C. M. J. Nat. Prod. 1988, 51, 675.
7. Krause, W.; Bohlmann, F. Tetrahedron Lett. 1987, 28, 2575.
8. Grimm, E. L.; Levac, S.; Coutu, M. L. Tetrahedron Lett. 1994, 35, 5369.
9. (a) Villagómez-Ibarra, R.; Joseph-Nathan, P. Tetrahedron Lett. 1994, 35, 4771.
10. (b) Villagómez-Ibarra, R.; Alvarez-Cisneros, C.; Joseph-Nathan, P. Tetrahedron 1995, 51, 9285.
11. Covarrubias, A.; Maldonado, L. A. 4th Chemical Congress of North America 1991, Abs. Org. 176.
12. (a) Stork, G.; Landesman, H. K. J. Am. Chem. Soc. 1956, 78, 5129.
13. (b) Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; Wiley: New York, 1967; Vol. 1, p 555.
14. For a review on the syntheses of cyclooctanes, which includes fragmentation reactions of bicyclic systems, see: Petasis, N. A.; Patane, M. A. Tetrahedron 1992, 48, 5757.
15. Johansson, A. M.; Mellin, Ch.; Hacksell, U. J. Org. Chem. 1986, 51, 5252.
16. For a reference in which a bicyclo[3.3.1]nonane pyrrolidinoke-tone closely related to 7 was isolated, but not characterized, see: Mitsuhashi, K.; Shiotani, S. Chem. Pharm. Bull. 1970, 18, 75.
17. 2 and CH protons are shown in the range of δ ≈1.0-4.0.
18. As a referee has pointed out, since the conversion 7 → 8 was followed only by TLC, an incomplete N-methylation reaction can also (partially) explain the observed results.
19. Aqueous acid treatment of bridged β-amino ketones gives bridged ketols by a reaction mechanism involving (1) acid-catalyzed opening of the bridged system, (2) hydrolysis of the immonium salt intermediate, and (3) acid-catalyzed aldol recyclization of the 1,5-keto aldehyde. See, for instance: (a) Allan, R. D.; Cordiner, B. G.; Wells, R. J. Tetrahedron Lett. 1968, 6055. (b) Momose, T.; Kinoshita, M.; Imanishi, T. Heterocycles 1979, 12, 243. (c) Boucher, R. J.; Campbell, M. M.; Rae, D. Tetrahedron 1990, 46, 6839.
20. Aqueous acid treatment of bridged β-amino ketones gives bridged ketols by a reaction mechanism involving (1) acid-catalyzed opening of the bridged system, (2) hydrolysis of the immonium salt intermediate, and (3) acid-catalyzed aldol recyclization of the 1,5-keto aldehyde. See, for instance: (a) Allan, R. D.; Cordiner, B. G.; Wells, R. J. Tetrahedron Lett. 1968, 6055. (b) Momose, T.; Kinoshita, M.; Imanishi, T. Heterocycles 1979, 12, 243. (c) Boucher, R. J.; Campbell, M. M.; Rae, D. Tetrahedron 1990, 46, 6839.
21. Aqueous acid treatment of bridged β-amino ketones gives bridged ketols by a reaction mechanism involving (1) acid-catalyzed opening of the bridged system, (2) hydrolysis of the immonium salt intermediate, and (3) acid-catalyzed aldol recyclization of the 1,5-keto aldehyde. See, for instance: (a) Allan, R. D.; Cordiner, B. G.; Wells, R. J. Tetrahedron Lett. 1968, 6055. (b) Momose, T.; Kinoshita, M.; Imanishi, T. Heterocycles 1979, 12, 243. (c) Boucher, R. J.; Campbell, M. M.; Rae, D. Tetrahedron 1990, 46, 6839.
22. Soriano-García, M.; Villena, R.; Covarrubias, A.; Olguin, J. S.; Maldonado, L. A. Acta Crystallogr. 1993, C49, 2140.
23. Hendrickson, J. B.; Boeckman, R. K., Jr. J. Am. Chem. Soc. 1971, 93, 1307.
24. Low-polarity compounds (unidentified) were also formed in this experiment. The successful (although modest yielding) formation of carboxylic acid 9a from the axial isomer 11a, very probably involves a nonconcerted carbonium ion initiated fragmentation. The alternative, concerted fragmentation of mesylate 11b from a boat ring C conformation is ruled out, since a strained (E)-cyclooctene double bond should be obtained.
25. Soriano-García, M.; Villena Iribe, R.; Covarrubias, A.; Cantú, F.; Maldonado, L. A. Anal. Sci. 1993, 9, 439.
26. Harrowven, D. C.; Pattenden, G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 3 pp 379-385 and references therein.
27. Soai, K.; Oyamada, H.; Takase, M.; Ookawa, A. Bull. Chem. Soc. Jpn. 1984, 57, 1948.
28. We thank M. Sc. José Agustín Guzmán, Institute de Investigaciones Químico Biológicas, Universidad Michoacana de San Nicolás Hidalgo, Morelia, Michoacán, México, for a generous gift of natural 1 and related spectral data.
29. Interestingly, cleavage of 13 with n-BuSNa in dry DMF gave a 7:3 mixture of 1 and 2 (95%).