A chiral base desymmetrisation - Ring-closing metathesis route to chiral azaspirocycles: Synthesis of core structures related to pinnaic acid and halichlorine

Synlett

Volumn , Issue 13, 2004, Pages 2295-2298

  Huxford, Timothy ^a   Simpkins, Nigel S ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

Author keywords

Azaspirocycle; Pinnaic acid; Ring closing metathesis

Indexed keywords

AZASPIROCYLIC COMPOUND; AZO COMPOUND; ESTER; HALICHLORINE; PINNAIC ACID; PIPERIDINE DERIVATIVE; SPIRO COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHIRALITY; CLAISEN REARRANGEMENT; DESYMMETRIZATION; GRIGNARD REACTION; RING CLOSING METATHESIS; SYNTHESIS;

EID: 8644271648     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2004-831335     Document Type: Article

References (29)

1. For leading references to histrionicotoxin, see: Stockman, R. A.; Sinclair, A.; Arini, L. G.; Szeto, P.; Hughes, D. L. J. Org. Chem. 2004, 69, 1598.
2. (a) Chou, T.; Kuramoto, M.; Otani, Y.; Shikano, M.; Yazawa, K.; Uemura, D. Tetrahedron Lett. 1996, 37, 3871.
3. (b) Carson, W.; Kim, G.; Hentemann, M. F.; Trauner, D.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2001, 40, 4450.
4. (c) Carson, M. W.; Kim, G.; Hentemann, M. F.; Trauner, D.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2001, 40, 4453.
5. (a) Kuramoto, M.; Tong, C.; Yamada, K.; Chiba, T.; Hayashi, Y.; Uemura, D. Tetrahedron Lett. 1996, 37, 3867.
6. (b) Trauner, D.; Schwartz, J. B.; Danishefsky, S. J. Angew. Chem. Int. Ed. 1999, 38, 3542.
7. (c) Trauner, D.; Danishefsky, S. J. Tetrahedron Lett. 1999, 40, 6513.
8. (d) Trauner, D.; Churchill, D. G.; Danishefsky, S. J. Helv. Chim. Acta 2000, 83, 2344.
9. For very recent formal syntheses of both (±)-halichlorine and (±)-pinnaic acid, and further references, see: Matsumura, Y.; Aoyagi, S.; Kibayashi, C. Org. Lett. 2004, 6, 965.
10. For varied approaches, see for example: (a) Willand, N.; Beghyn, T.; Nowogrocki, G.; Gesquire, J.-C.; Deprez, B. Tetrahedron Lett. 2004, 45, 1051.
11. (b) Canesi, S.; Belmont, P.; Bouchu, D.; Rousset, L.; Ciufolini, M. A. Tetrahedron Lett. 2002, 43, 5193.
12. (c) Ciblat, S.; Canet, J.-L.; Troin, Y. Tetrahedron Lett. 2001, 42, 4815.
13. For methods based on ring closing metathesis, see: (a) Wright, D. L.; Schulte, J. P. II.; Page, M. A. Org. Lett. 2000, 2, 1847.
14. (b) Suga, S.; Watanabe, M.; Yoshida, J. J. Am. Chem. Soc. 2002, 124, 14824.
15. (c) Nieczypor, P.; Mol, J. C.; Bespalova, N. B.; Bubnov, Y. N. Eur. J. Org. Chem. 2004, 812.
16. (d) Edwards, A. S.; Wybrow, R. A. J.; Johnstone, C.; Adams, H.; Harrity, J. P. A. Chem. Commun. 2002, 1542.
17. (e) Wybrow, R. A. J.; Stevenson, N. G.; Harrity, J. P. A. Synlett 2004, 140.
18. Goldspink, N. J.; Simpkins, N. S.; Beckmann, M. Synlett 1999, 1292.
19. Clive has also recognised the possibility of applying our chiral base reaction to this problem, see: Yu, M.; Clive, D. L. J.; Yeh, V. S. C.; Kang, S.; Wang, J. Tetrahedron Lett. 2004, 45, 2879.
20. In ref.8, Clive reports only a 69% ee was possible in the preparation of 7, whereas we have observed 90-95% ee in several runs. We are presently in communication with Professor Clive in order to resolve this disparity.
21. Langer, F.; Schwink, L.; Devasagayaraj, A.; Chavant, P.-Y.; Knochel, P. J. Org. Chem. 1996, 61, 8229.
22. For reviews, see: (a) Wipf, P.; Jahn, H. Tetrahedron 1996, 52, 12853.
23. (b) Wipf, P.; Xu, W.; Smitrovich, J. H.; Lehmann, R.; Venanzi, L. M. Tetrahedron 1994, 50, 1935.
24. 2Ph group.
25. Analysis of allylic alcohol 10, in the form of its 4-nitrobenzoate ester revealed the stereochemistry shown. We thank Dr A. J. Blake of this school for this result, full details of which will be published later.
26. 2Si [M + H]: 512.2985; found: 512.2999.
27. 3Si [M + H]: 582.3403; found: 582.3398.
28. Martin Castro, A. M. Chem. Rev. 2004, 104, 2939.
29. 2Et substituent was seen.