A short synthesis of 10-hydroxy 7-spirocyclopropanated camphor

Journal of Organic Chemistry

Volumn 70, Issue 20, 2005, Pages 8224-8227

  Yang, Yu Rong ^a   Li, Wei Dong Z ^a,b  

^a LANZHOU UNIVERSITY   (China)

^b NANKAI UNIVERSITY   (China)

Author keywords

[No Author keywords available]

Indexed keywords

10 HYDROXY 7 SPIROCYCLOPROPANATED CAMPHOR; 2 CHLOROACRYLONITRILE; 4 BENZYL OXYMTHYLSPIRO[2.4]HEPTA 4,6 DIENE; ACRYLONITRILE; CAMPHOR DERIVATIVE; CYCLOPENTADIENE DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CHEMICAL STRUCTURE; CYCLOADDITION; DIELS ALDER REACTION; SYNTHESIS;

EID: 25444519527     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0509962     Document Type: Article

References (24)

1. Li, W.-D. Z.; Yang, Y.-R. Org. Lett. 2005, 7, 3107.
2. Föhlisch, B.; Bakr, D. A.; Fischer, P. J. Org. Chem. 2002, 67, 3682.
3. For some other relevant applications in synthesis, see: (a) Corey, E. J.; Shiner, C. S.; Volante, R. P.; Cyr, C. R. Tetrahedron Lett. 1975, 17, 1161.
4. (b) Starr, J. T.; Koch, G.; Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 8793.
5. (c) Antczak, K.; Kingston, J. F.; Fallis, A. G. Can. J. Chem. 1985, 63, 993.
6. (d) Attah-Poku, S. K.; Anticzak, K.; Alward, S. J.; Fallis, A. G. Can. J. Chem. 1984, 62, 1717.
7. (e) Anticzak, K.; Kingston, J. F.; Fallis, A. G.; Hanson, A. W. Can. J. Chem. 1987, 65, 114.
8. For relevant spiro-cyclopropyl derivatives used in mechanistic studies, see: (f) Wilcox, C. F., Jr.; Jesaitis, R. G. Tetrahedron Lett. 1967, 9, 2567.
9. (g) Lenoir, D.; Schleyer, P. R.; Ipaktschi, J. Liebigs Ann. Chem. 1971, 750, 28.
10. (h) Kende, A. S.; Jenkins, J. K.; Friedrich, L. E. J. Chem. Soc., Chem. Commun. 1971, 1215.
11. For an alternative spiro-cyclopropanation method via a carbene species derived from diazocyclopentadiene, see: Moss, R. A. J. Chem. Soc., Chem. Commun. 1965, 622.
12. Cf.: (a) Corey, E. J.; Weinshenker, N. M.; Schaaf, T. K.; Huber, W. J. Am. Chem. Soc. 1969, 91, 5675.
13. (b) Corey, E. J.; Koelliker, U.; Neuffer, J. J. Am. Chem. Soc. 1971, 93, 1489.
14. Better yield was achieved with this alkylating agent.
15. 1H NMR analysis of the crude product. The major desired product 6a might be derived from the predominating chelated form of metal cyclopentadienide as shown below. For some regiodegenerated alkylation (or cyclopropanation) of alkyl-substituted cyclopentadienes, see: (a) Alder, K.; Ache, H. J.; Flock, F. H. Chem. Ber. 1960, 93, 1888.
16. (b) Meyer, F.; Haynes, P.; McLean, S.; Harrison, A. G. Can. J. Chem. 1965, 43, 211.
17. (c) McLean, S.; Haynes, P. Tetrahedron 1965, 21, 2313.
18. (d) Clark, R. A.; Hayles, W. J.; Youngs, D. S. J. Am. Chem. Soc. 1975, 97, 1966. We thank one of the reviewers for bringing these references to our attention. (Diagram presented)
19. Satisfactory spectral data were obtained, respectively; see Experimental Section for details.
20. 2(all data) = 0.1056. See CIF file in the Supporting Information for more details.
21. An attempted cyclopropane-participated oxy-Cope rearrangement of I to II was not observed due probably to the poor orbital alignment required for this electrocyclic reaction, presumably beacuse of the tremendous inherent ring strain in I. (Diagram presented)
22. The exo-hydroxy epimer of 12 was partially recovered under similar reaction conditions.
23. For a review, see: Money, T. Nat. Prod. Rep. 1985, 253.
24. For general experimental procedures, see the Supporting Information of ref 1.