A new entry to oxacycles via base-catalyzed endo mode cyclization of allenyl sulfoxides and sulfones

Organic Letters

Volumn 3, Issue 21, 2001, Pages 3385-3387

  Mukai, Chisato ^a   Yamashita, Haruhisa ^a   Hanaoka, Miyoji ^a  

^a KANAZAWA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BIOLOGICAL FACTOR; ETHER DERIVATIVE; SULFONE; SULFOXIDE;

ARTICLE; CATALYSIS; CHEMISTRY; COMBINATORIAL CHEMISTRY; CYCLIZATION; SYNTHESIS;

BIOLOGICAL FACTORS; CATALYSIS; COMBINATORIAL CHEMISTRY TECHNIQUES; CYCLIZATION; ETHERS, CYCLIC; SULFONES; SULFOXIDES;

EID: 0035909599     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0101842     Document Type: Article

References (24)

1. (a) Shimizu, Y. Marine Natural Products; Academic Press: New York, 1978, Vol. 1.
2. (b) Moore, R. E. Marine Natural Products: Chemical and Biological Perspectives; Scheuer, P. J., Ed.; Academic Press: New York, 1978, Vol. 2.
3. (c) Faulkner, D. J. Nat. Prod. Rep. 1986, 3, 1.
4. (d) Yasumoto, T.; Murata, M. Chem. Rev. 1993, 93, 1897.
5. (e) Faulkner, D. J. Nat. Prod. Rep. 1996, 13, 75.
6. (a) Mukai, C.; Ikeda, Y.; Sugimoto, Y.; Hanaoka, M. Tetrahedron Lett. 1994, 35, 2179.
7. (b) Mukai, C.; Sugimoto, Y. Ikeda, Y.; Hanaoka, M. J. Chem. Soc., Chem. Commun. 1994, 1161.
8. (c) Mukai, C.; Sugimoto, Y.; Ikeda, Y.; Hanaoka, N. Tetrahedron 1998, 54, 823.
9. (d) Mukai, C.; Yamaguchi, S.; Sugimoto, Y.; Miyakoshi, N.; Kasamatsu, E.; Hanaoka, M. J. Org. Chem. 2000, 65, 6761.
10. (e) Mukai, C.; Yamaguchi, S.; Kim, I. J.; Hanaoka, M. Chem. Pharm. Bull. 2001, 49, 613.
11. Mukai, C.; Yamashita, H.; Ichiryu, T.; Hanaoka, M. Tetrahedron 2000, 56, 2203.
12. Numbering was based on the allene skeleton for convenience.
13. Denmark reported intramolecular reaction of allenyl sulfones with alkoxides: Denmark, S, E.; Harmata, M. A.; White, K. S. J. Org. Chem. 1987, 52, 4031.
14. 4 under basic conditions resulted in the formation of the five-and six-membered oxacycles (benzofuran and pyran derivatives, respectively): (a) Pairaudeau, G.; Parsons, P. J.; Underwood, J. M. J. Chem. Soc., Chem. Commun. 1987, 1718.
15. (b) Gray, M.; Parsons, P. J.; Neary, A. P. Synlett 1992, 597.
16. Dai described an exo mode cyclization of the allenyl sulfone derivatives leading to compounds having a furan framework: Dai, W.-M.; Lee, Y. H. Tetrahedron 1998, 54, 12497.
17. Homer, L.; Binder, V. Ann. Chem. 1972, 37, 757.
18. tBuOK.
19. The corresponding exo methylene derivative could not be detected in the reaction mixture.
20. The sulfonyl derivatives, 8 and 9, were synthesized according to the procedure described for the preparation of 5.
21. The stereochemistry of 10 was determined on the basis of an NOE experiment. Irradiation of H-3 diagnostically showed 6.0% enhancement of the methyl protons and no enhancement of the vinyl proton. On the other hand, 8.8% enhancement of the methyl protons was confirmed, while no enhancement of H-3 could be detected upon irradiation of the vinyl proton.
22. No endo methylene derivatives could be isolated. It should be mentioned that no isomerization was observed when 7d, 10, and 11 were independently exposed to the standard basic conditions and the staring materials were completely recovered intact.
23. The fact that irradiation of the benzylidene proton produced 6.3% enhancement of H-8 while no enhancement of H-3 could be detected in its NOE experiment strongly supported the (E)-structure of 11.
24. The starting 12 and 13 were prepared from the corresponding propynyl alcohol derivatives according to the procedure described for the preparation of 4 and 5.