Synthetic applications of 2-(1,3-dithian-2-yl)indoles. 7. Synthesis of aspidospermidine

Journal of Organic Chemistry

Volumn 61, Issue 22, 1996, Pages 7882-7888

  Forns, Pilar ^a   Diez, Anna ^a   Rubiralta, Mario ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ASPIDOSPERMIDINE; INDOLE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0029801252     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9609900     Document Type: Article

References (23)

1. Part 6: Forns, P.; Diez, A.; Rubiralta, M.; Solans, X.; Font-Bardía, M. Tetrahedron 1996, 52, 3563-3574.
2. 3-piperidein-2-one as the piperidine synthon: Micouin, L.; Diez, A.; Castells, J.; López, D.; Rubiralta, M.; Quirion, J.-C.; Husson, H.-P. Tetrahedron. Lett. 1995, 36, 1693-1696.
3. 3-piperidein-2-one as the electrophile: Diez, A.; Castells, J.; Forns, P.; Rubiralta, M.; Grierson, D. S.; Husson H.-P.; Solans, X.; Font-Bardía, M. Tetrahedron 1994, 50, 6585-6602.
4. (c) Using 1-methyl- or 1-benzyl-3-ethyl-3,4-epoxypiperidine as the electrophile: Rubiralta, M.; Torrens, A.; Reig, I. Heterocycles 1989, 29, 2121-2133.
5. For the closure of ring E in the Strychnos series via Pummerer reaction, see: Amat, M.; Bosch, J. J. Org. Chem. 1992, 57, 5792-5796.
6. (a) Saxton, J. E. The Aspidospermine Group. In The Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; John Wiley and Sons, Inc.: New York, 1983; Vol. 25, Part 4, pp 331-437;
7. (b) 1994; Vol. 25, Supplement to Part 4, pp 357-436.
8. For the synthesis of aspidospermidine by closure of ring E through a Pummerer reaction on the [ABCD] framework, in turn constructed by an intramolecular Diels-Alder reaction, see: Exon, C.; Gallagher, T.; Magnus, P. J. Am. Chem. Soc. 1983, 105, 4739-4749.
9. For the synthesis of 18-noraspidospermidine by construction of ring E via Pummerer reaction on the pyridocarbazole nucleus, prepared by closure of ring D via an azide, see: Desmaele, D.; D'Angelo, J. Tetrahedron Lett. 1990, 31, 883-886.
10. For the synthesis of aspidospermidine by construction of ring E with ethylene bromide from the pyridocarbazole nucleus, built from a 2-(3-indolyl)piperidine-3-acetate, see: Wenkert, E.; Hudlicky, T. J. Org. Chem. 1988, 53, 1953-1957.
11. For the synthesis of deethylaspidospermidine from the [ABCD] ring system, built by closure of ring C from a 2-(3-indolyl)piperidine-3-acetate, see: Natsume, M.; Utsunomiya, I. Heterocycles 1982, 17, 111-115.
12. For the synthesis of pyridocarbazole derivatives by intramolecular cyclization of an iminium salt, see: (a) Joule, J. A.; Salas, M.-L. J. Chem. Res., Miniprint 1990, 664-673. (b) Troin, Y.; Diez, A.; Bettiol, J.-L.; Rubiralta, M.; Grierson, D. S.; Husson, H.-P. Heterocycles 1991, 32, 663-668.
13. For the synthesis of pyridocarbazole derivatives by intramolecular cyclization of an iminium salt, see: (a) Joule, J. A.; Salas, M.-L. J. Chem. Res., Miniprint 1990, 664-673. (b) Troin, Y.; Diez, A.; Bettiol, J.-L.; Rubiralta, M.; Grierson, D. S.; Husson, H.-P. Heterocycles 1991, 32, 663-668.
14. (a) See ref 8.
15. (b) Rubiralta, M.; Diez, A.; Bosch, J.; Solans, X. J. Org. Chem. 1989, 54, 5591-5597.
16. (c) López, I.; Diez, A.; Rubiralta, M. Tetrahedron 1996, 52, 000.
17. Lee, D. L.; Morrow, C. J.; Rapoport, H. J. Org. Chem. 1974, 39, 893-902.
18. Stork, G.; Zhao, K. Tetrahedron Lett. 1989, 30, 287-290.
19. Grobelny, D.; Máslak, P.; Witck, S. Tetrahedron Lett. 1979, 2639.
20. For the biogenetic numbering, see: (a) Southon, I. W.; Buckingham, J. Dictionary of Alkaloids; Chapman and Hall: London, 1989; p xxxviii. The biogenetic numbering is used in this paper when referring to Aspidosperma-type compounds 1, 24, and 25.
21. Le Ménez, P.; Kunesch, N.; Liu, S.; Wenkert, E. J. Org. Chem. 1991, 56, 2915-2918.
22. The N-alkylation of pyridine during its Raney Ni reduction in EtOH is well known: Morlacchi, F.; Losacco, V.; Tortorella, V. J. Heterocycl. Chem. 1979, 16, 297-299 and references cited therein.
23. For the NMR data of this compound, see the supporting information.