A new solution for the construction of the piperidine ring of Strychnos alkaloids from 3a-(o-nitrophenyl)hexahydroindol-4-ones. Total syntheses of (±)-tubifolidine, (±)-dihydroakuammicine, and (±)-akuammicine

Tetrahedron Letters

Volumn 37, Issue 29, 1996, Pages 5213-5216

  Solé, Daniel ^a   Bonjoch, Josep ^a   García Rubio, Silvina ^a   Suriol, Ramon ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AKUAMMICINE; ALKALOID; DIHYDROAKUAMMICINE; KETONE; PIPERIDINE; SILANE DERIVATIVE; TUBIFOLIDINE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; SYNTHESIS;

STAPHYLOCOCCUS PHAGE 3A; STRYCHNOS;

EID: 0030586102     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01054-4     Document Type: Article

References (32)

1. 1. (a) Solé, D.; Bonjoch, J. Tetrahedron Lett. 1991, 32, 5183-5183.
2. (b) Solé, D.; Bosch, J.; Bonjoch, J. Tetrahedron 1996, 52, 4013-4028.
3. 2. For recent reviews, see: (a) Sapi, J.; Massiot, G. In Monoterpenoid Indole Alkaloids, Saxton J.E., Ed. In The Chemistry of Heterocyclic Compounds, Taylor, E.C., Ed. Supplement to Vol. 25, Part 4, pp 279-355, Wiley: New York, 1994.
4. 2. For recent reviews, see: (a) Sapi, J.; Massiot, G. In Monoterpenoid Indole Alkaloids, Saxton J.E., Ed. In The Chemistry of Heterocyclic Compounds, Taylor, E.C., Ed. Supplement to Vol. 25, Part 4, pp 279-355, Wiley: New York, 1994.
5. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids, Cordell, G.A., Ed., Vol. 48, pp 75-189, Academic Press: New York, 1996.
6. 3. Bonjoch, J.; Solé, D.; Bosch, J. J. Am. Chem. Soc. 1993, 115, 2064-2065.
7. 4. The biogenetic numbering and ring labeling is used throughout this paper: Le Men, J.; Taylor, W.I. Experientia 1965, 21, 508-510.
8. 5. (a) Bonjoch, J.; Solé, D.; Bosch, J. J. Am. Chem. Soc. 1995, 117, 11017-11018.
9. (b) Solé, D.; Bonjoch, J.; Bosch, J. J. Org Chem. 1996, 61, in press.
10. 6. For other synthesis of Strychnos alkaloids involving the formation of this strategic bond: (a) Rawal, V.H.; Michoud, C.; Monestel, R.F. J. Am. Chem. Soc. 1993, 115, 3030-3031.
11. (b) Rawal, V.H.; Iwasa, S.; Michoud, C. J. Org. Chem. 1994, 59, 2685-2686.
12. (c) Kuehne, M.E.; Wang, T.; Seraphin, D.; Synlett. 1995, 557-558.
13. (d) Stork, G. Presented at the Ischia Advanced School of Organic Chemistry, Ischia Porto, Italy, September 21, 1992. We thank Professor Gilbert Stork for sending us a detailed scheme of his synthesis of strychnine.
14. 7. For the intramolecular addition of propargylic silanes to enones, see Schinzer, D. Synthesis 1988, 263-273.
15. 8. (a) Mastalerz, H. J. Org. Chem. 1984, 49, 4092-4094.
16. (b) Klaver, W.J.; Moolenaar, M.J.; Hiemstra, H.; Speckamp, W.N. Tetrahedron 1988, 44, 3805-3818.
17. 3 310.1325, found 310.1317.
18. 10. All yields are from material purified by column chromatography. Satisfactory analytical and spectroscopic data were obtained for all new compounds.
19. 11. For the use of propargylic silanes in the synthesis of other azabicyclo derivatives, see: (a) Hiemstra, H.; Klaver, W.J.; Speckamp, W.N. Recl. Trav. Chim. Pays-Bas 1986, 105, 299-306.
20. (b) Klaver, W.J.; Hiemstra, H.; Speckamp, W.N. J. Am. Chem. Soc. 1989, 111, 2588-2595.
21. 13C NMR spectral data with those previously reported: Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299-6312.
22. 13. For previous total syntheses of tubifolidine, see: (a) Dadson, B.A.; Harley-Mason, J.; Foster, G.H. J. Chem. Soc., Chem. Commun. 1968, 1233.
23. (b) Ban, Y.; Yoshida, K.; Goto, J.; Oishi, T.; Takeda, E. Tetrahedron 1983, 39, 3657-3668. See also references 3 and 12.
24. a-ethyltubifolidine was isolated as the major product (20%).
25. 15. Angle, S.R.; Fevig, J.M.; Knight, S.D.; Marquis, R.W., Jr.; Overman, L.E. J. Am. Chem. Soc. 1993, 115, 3966-3977. See also reference 3.
26. -1.
27. 17. The corresponding O-acylated product was formed in ≈ 5% yield in some runs. Unreacted starting ketone was recovered to a considerable extent (30%).
28. 18. For the only previous synthesis of 19,20-dihydroakuammicine, see reference 12.
29. 1H NMR (300 MHz) spectral data with those reported for the natural product: (a) Hu, W.-L.; Zhu, J.-P.; Hesse, M. Planta Med. 1989, 55, 463-466.
30. f values of our synthetic akuammicine in several solvent mixtures were also coincident with those of an authentic sample of the alkaloid kindly provided by Professor Georges Massiot (University of Reims).
31. 20. For previous syntheses of this racemic alkaloid, see references 5b, 15, and 19b.
32. 21. Knight, S.D.; Overman, L.E.; Pairaudeau, G. J. Am. Chem. Soc. 1995, 117, 5776-5788. See also references 3, 5, and 15.