Total synthesis of indole alkaloids of the ervatamine group. A biomimetic approach

Journal of Organic Chemistry

Volumn 61, Issue 6, 1996, Pages 1916-1917

  Bennasar, M Lluïsa ^a   Vidal, Bernat ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ERVATAMINE; INDOLE ALKALOID; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029983798     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9600058     Document Type: Article

References (27)

1. (a) Joule, J. A. Indoles, The Monoterpenoid Indole Alkaloids. In The Chemistry of Heterocyclic Compounds; Saxton, J. E., Weissberger, A., Taylor, E. C., Eds.; Wiley: New York, 1983; Vol. 25, Part 4, pp 232-239.
2. (b) Alvarez, M.; Joule, J. Monoterpenoid Indole Alkaloids. In The Chemistry of Heterocyclic Compounds; Saxton, J. E., Taylor, E. C., Eds.; Wiley: Chichester, 1994; Vol. 25, Supplement to Part 4, pp 234-236.
3. Knox, J. R.; Slobbe, J. Aust. J. Chem. 1975, 28, 1813 and 1825.
4. Bui, A.-M.; Debray, M.-M.; Boiteau, P.; Potier, P. Phytochemistry 1977, 16, 703.
5. Veechietti, V.; Ferrari, G.; Orsini, F.; Pelizzoni, F.; Zajotti, A. Phytochemistry 1978, 17, 835.
6. The biogenetic numbering is used throughout this paper for all tetracyclic compounds. Le Men, J.; Taylor, W. I. Experientia 1965, 21, 508.
7. The trans C/D ring junction is present in isomethuemne (16-epimethuenine) and 6-oxo-16-episilicine.
8. The biogenetic relationship between the alkaloids of the vobasine and ervatamine groups through an intermediate like A has been demonstrated: (a) Husson, A.; Langlois Y.; Riche, C.; Husson, H.-P.; Potier, P. Tetrahedron 1973, 29, 3095. (b) Thal, C.; Dufour, M.; Potier, P.; Jaouen, M.; Mansuy, D. J. Am. Chem. Soc. 1981, 103, 4956.
9. The biogenetic relationship between the alkaloids of the vobasine and ervatamine groups through an intermediate like A has been demonstrated: (a) Husson, A.; Langlois Y.; Riche, C.; Husson, H.-P.; Potier, P. Tetrahedron 1973, 29, 3095. (b) Thal, C.; Dufour, M.; Potier, P.; Jaouen, M.; Mansuy, D. J. Am. Chem. Soc. 1981, 103, 4956.
10. Husson, H.-P.; Bannai, K.; Freire, R.; Mompon, B.; Reis, F. A. M. Tetrahedron 1978, 34, 1363.
11. (a) Langlois, Y.; Potier, P. Tetrahedron 1975, 31, 423.
12. (b) Grierson, D. S.; Bettiol, J.-L.; Buck, I.; Husson, H.-P.; Rubiralta, M.; Diez, A. J. Org. Chem. 1992, 57, 6414.
13. Bennasar, M.-L.; Vidal, B.; Bosch, J. J. Org. Chem. 1995, 60, 4280.
14. For a recent review on the nueleophilic addition of indole-containing enolates to pyridinium salts and its application to the synthesis of bridged indole alkaloids, see: Bosch, J.; Bennasar, M.-L. Synlett 1995, 587.
15. The addition of stabilized carbon nucleophiles to N-alkyl-β-acylpyridinium salts for alkaloid synthesis was first used by Wenkert: (a) Wenkert, E. Pure Appl. Chem. 1981, 53, 1271. (b) Wenkert, E.; Guo, M.; Pestchanker, M. J. ; Shi, Y.-J.; Vankar, Y. D. J. Org. Chem. 1989, 54, 1166 and references cited therein. See also: (c) Spitzner, D.; Arnold. K; Stezowski, J. J.; Hildenbrand, T.; Henkel, S. Chem. Ber. 1989, 122, 2027. (d) Amann, R.; Spitzner, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 1320.
16. The addition of stabilized carbon nucleophiles to N-alkyl-β-acylpyridinium salts for alkaloid synthesis was first used by Wenkert: (a) Wenkert, E. Pure Appl. Chem. 1981, 53, 1271. (b) Wenkert, E.; Guo, M.; Pestchanker, M. J. ; Shi, Y.-J.; Vankar, Y. D. J. Org. Chem. 1989, 54, 1166 and references cited therein. See also: (c) Spitzner, D.; Arnold. K; Stezowski, J. J.; Hildenbrand, T.; Henkel, S. Chem. Ber. 1989, 122, 2027. (d) Amann, R.; Spitzner, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 1320.
17. The addition of stabilized carbon nucleophiles to N-alkyl-β-acylpyridinium salts for alkaloid synthesis was first used by Wenkert: (a) Wenkert, E. Pure Appl. Chem. 1981, 53, 1271. (b) Wenkert, E.; Guo, M.; Pestchanker, M. J. ; Shi, Y.-J.; Vankar, Y. D. J. Org. Chem. 1989, 54, 1166 and references cited therein. See also: (c) Spitzner, D.; Arnold. K; Stezowski, J. J.; Hildenbrand, T.; Henkel, S. Chem. Ber. 1989, 122, 2027. (d) Amann, R.; Spitzner, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 1320.
18. The addition of stabilized carbon nucleophiles to N-alkyl-β-acylpyridinium salts for alkaloid synthesis was first used by Wenkert: (a) Wenkert, E. Pure Appl. Chem. 1981, 53, 1271. (b) Wenkert, E.; Guo, M.; Pestchanker, M. J. ; Shi, Y.-J.; Vankar, Y. D. J. Org. Chem. 1989, 54, 1166 and references cited therein. See also: (c) Spitzner, D.; Arnold. K; Stezowski, J. J.; Hildenbrand, T.; Henkel, S. Chem. Ber. 1989, 122, 2027. (d) Amann, R.; Spitzner, D. Angew. Chem., Int. Ed. Engl. 1991, 30, 1320.
19. 2) 2-acetylindoles was also unsuccessful.
20. All yields are from material purified by column chromatography. Satisfactory analytical and spectral data were obtained from all new compounds.
21. Concomitant reduction of the acetyl group was observed when pure MeOH was used as the solvent for the hydrogenation.
22. The isomeric cis-tetrahydropyridine resulting from reduction of the vinylogous urethane double bond was isolated as a minor byproduct (13% yield).
23. Murakami, Y.; Watanabe, T.; Kobayashi, A.; Yokoyama, Y. Synthesis 1984, 738.
24. Clivio, P.; Richard, B.; Zeches, M.; Le Men-Olivier, M.; Goh, S. H.; David, B.; Sevenet, T. Phytochemistry 1990, 29, 2693.
25. For the use of this methodology in a biomimetic synthesis of ervitsine, see: Bennasar, M.-L.; Vidal, B.; Bosch, J. J. Am. Chem. Soc. 1993, 115, 5340.
26. There are very few examples of the reduction of 1,4-dihydropyridines generated by nucleophilic addition to N-alkylpyridinium salts: (a) Lounasmaa, M.; Koskinen, A. Tetrahedron Lett. 1982, 23, 349. (b) Lavilla, R.; Gotsens, T.; Gullón, F.; Bosch, J Tetrahedron 1994, 50, 5233.
27. There are very few examples of the reduction of 1,4-dihydropyridines generated by nucleophilic addition to N-alkylpyridinium salts: (a) Lounasmaa, M.; Koskinen, A. Tetrahedron Lett. 1982, 23, 349. (b) Lavilla, R.; Gotsens, T.; Gullón, F.; Bosch, J Tetrahedron 1994, 50, 5233.