Tandem double intramolecular [4 + 2]/[3 + 2] cycloadditions of nitroalkenes

Organic Letters

Volumn 3, Issue 18, 2001, Pages 2907-2910

  Denmark, Scott E ^a   Baiazitov, Ramil Y ^a   Nguyen, Son T ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; NITRO DERIVATIVE; POLYENE;

ARTICLE; CHEMISTRY; CONFORMATION;

ALKENES; MOLECULAR CONFORMATION; NITRO COMPOUNDS; POLYENES;

EID: 0035817994     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016385n     Document Type: Article

References (30)

1. (a) Ho, T.-L. Tandem Organic Reactions; Wiley: New York, 1992.
2. (b) Ziegler, F. E. In Comprhensive Organic Synthesis, Combining C-C p-Bonds; Paquette, L. A., Ed.; Pergamon Press: Oxford, 1991; Vol. 5, Chapter 7.3.
3. (c) Tietze, L. F.; Beifuss, U. A. Angew. Chem., Int. Ed. Engl. 1993, 32, 131.
4. (d)Grigg, R., Ed. Cascade Reactions; Tetrahedron Symposium in Print; Elsevier: New York, 1996; No. 62.
5. (a) Denmark, S. E.; Thorarensen, A. Chem. Rev. 1996, 96, 137.
6. (b) Denmark, S. E.; Thorarensen, A.; Middleton, D. S. J. Am. Chem. Soc. 1996, 118, 8266.
7. (c) Denmark, S. E.; Thorarensen, A. J. Am. Chem. Soc. 1997, 119, 125.
8. (d) Denmark, S. E.; Hurd, A. R.; Sacha, H. J. J. Org. Chem. 1997, 62, 1668.
9. (e) Denmark, S. E.; Marcin, L. R. J. Org. Chem. 1997, 62, 1675.
10. (g) Denmark, S. E.; Dixon, J. A. J. Org. Chem. 1997, 62, 7086.
11. (h) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046.
12. (a) Denmark, S. E.; Hurd, A. R. J. Org. Chem. 1998, 63, 3045.
13. (b) Denmark, S. E.; Thorarensen, A. J. Org. Chem. 1994, 59, 5672.
14. (c) Denmark, S. E.; Herbert, B. J. Am. Chem. Soc. 1998, 120, 7357.
15. (d) Denmark, S. E.; Hurd, A. R. J. Org. Chem. 2000, 65, 2875.
16. (e) Denmark, S. E.; Herbert, B. J. Org. Chem. 2000, 65, 2887.
17. (a) Denmark, S. E.; Stolle, A.; Dixon, J. A.; Guagnano, V. J. Am. Chem. Soc. 1995, 117, 2100.
18. (b) Denmark, S. E.; Schnute, M. E.; Marcin, L. R.; Thorarensen, A. J. Org. Chem. 1995, 60, 3205.
19. (c) Denmark, S. E.; Guagnano, V.; Dixon, J. A.; Stolle, A. J. Org. Chem. 1997, 62, 4610.
20. (d) Denmark, S. E.; Dixon, J. A. J. Org. Chem. 1997, 62, 7086.
21. (e) Denmark, S. E.; Middleton, D. S. J. Org. Chem. 1998, 63, 1604.
22. For an early study on the tandem double intramolecular cycloaddition in a fused/fused mode, see: Moon, Y. C. Ph.D. Thesis, University of Illinois, Urbana, 1991.
23. These nitroalkenes were both prepared in nine steps from cyclohexene. See Supporting Information.
24. Denmark, S. E.; Moon, Y.-C.; Cramer, C. J.; Dappen, M. S.; Senanayake, C. B. W. Tetrahedron 1990, 46, 7373.
25. (a) Padwa, A. In 1,3-DipolarCyloaddition Chemistry; Padwa, A., Ed.; Wiley-Interscience: New York, 1984; Vol. 2, Chapter 12.
26. (b) Confalone, P. N.; Huie, E. M. Org. React. 1988, 36, 1.
27. 4 to provide the nitronate in 82% yield. However, reaction of the nitronate bearing a cis dipolarophile in the [3 + 2] cycloaddition was found to be still slower than that of 4. Heating the nitronate in toluene at 100°C for 3 days provided the nitroso acetal in 23% yield and 68% of recovered starting material. The effects of dipolarophile geometry on the rate of the intramolecular [3 + 2] cycloaddition of cyclic nitronates has been previously observed. (a) Denmark, S. E.; Senanayake, C. B. W. Tetrahedron 1996, 52, 11579.
28. (b) Denmark, S. E.; Seierstad, M. J.; Herbert, B. J. Org. Chem. 1999, 64, 884.
29. Nitroalkenes 6 and 9 were prepared in 10 and 11 steps, respectively, starting from caprolactone. See Supporting Information.
30. Denmark, S. E.; Dixon, J. A. J. Org. Chem. 1998, 63, 6178.