Divergent Diastereoselectivity in the Addition of Nucleophiles to Five-Membered-Ring Oxonium Ions

Journal of Organic Chemistry

Volumn 62, Issue 20, 1997, Pages 6706-6707

  Shaw, Jared T ^a   Woerpel, K A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001640238     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971208e     Document Type: Article

References (25)

1. Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry; Pergamon: New York, 1983; pp 209-221.
2. Holmes, C. P.; Bartlett, P. A. J. Org. Chem. 1989, 54, 98-108.
3. Davis, A. P.; Hegarty, S. C. J. Am. Chem. Soc. 1992, 114, 2745-2746.
4. Rychnovsky, S. D.; Skalitzky, D. J. Synlett 1995, 555-556.
5. Boons, G.-J.; Eveson, R.; Smith, S.; Stauch, T. Synlett 1996, 536-537
6. Rychnovsky, S. D.; Dahanukar, V. H. J. Org. Chem. 1996, 61, 7648-7649.
7. Stewart, A. O.; Williams, R. M. J. Am. Chem. Soc. 1985, 107, 4289-4296.
8. Araki, Y.; Kobayashi, N.; Ishido, Y. Carbohyd. Res. 1987, 171, 125-139
9. Mukaiyama, T.; Shimpuku, T.; Takashima, T.; Kobayashi, S. Chem. Lett. 1989, 145-148.
10. Schmitt, A.; Reissig, H.-U. Synlett 1990, 40-42. See also: Schmitt, A.; Reissig, H.-U. Chem. Ber. 1995, 128, 871-876.
11. Schmitt, A.; Reissig, H.-U. Synlett 1990, 40-42. See also: Schmitt, A.; Reissig, H.-U. Chem. Ber. 1995, 128, 871-876.
12. Alonso, E.; Ramon, D. J.; Yus, M. Tetrahedron 1997, 53, 2641-2652.
13. Shaw, J. T.; Woerpel, K. A. J. Org. Chem. 1997, 62, 442-443.
14. Shaw, J. T.; Woerpel, K. A. Tetrahedron 1997, in press.
15. Eliel, E. L.; Frye, S. V.; Hortelano, E. R.; Chen, X.; Bai, X. Pure Appl Chem. 1991, 63, 1591-1598.
16. The terms "alpha" and "beta" are used in this paper to denote the relative positions between the electrophilic carbon atom and the substituents on the ring.
17. Control experiments confirmed that oxonium ion 2 was the reactive intermediate in this acetal substitution reaction; the details are provided as Supporting Information. For discussions of the mechanism of Lewis acid promoted acetal substitutions, see, for example: (a) Mori, I.; Ishihara, K.; Flippin, L. A.; Nozaki, K.; Yamamoto, H.; Bartlett, P. A.; Heathcock, C. H. J. Org. Chem. 1990, 55, 6107-6115. (b) Denmark, S. E.; Almstead, N. G. J. Org. Chem. 1991, 56, 6458-6467.
18. Control experiments confirmed that oxonium ion 2 was the reactive intermediate in this acetal substitution reaction; the details are provided as Supporting Information. For discussions of the mechanism of Lewis acid promoted acetal substitutions, see, for example: (a) Mori, I.; Ishihara, K.; Flippin, L. A.; Nozaki, K.; Yamamoto, H.; Bartlett, P. A.; Heathcock, C. H. J. Org. Chem. 1990, 55, 6107-6115. (b) Denmark, S. E.; Almstead, N. G. J. Org. Chem. 1991, 56, 6458-6467.
19. 4-mediated reaction of dimethyl acetals proceeds through an oxonium ion intermediate: Sammakia, T.; Smith, R. S. J. Am. Chem. Soc. 1994, 116, 7915-7916.
20. Acyclic alkoxyalkyl acetates undergo substitution reactions via oxonium ion intermediates: Matsutani, H.; Ichikawa, S.; Yaruva, J.; Kusumoto, T.; Hiyama, T. J. Am. Chem. Soc. 1997, 119, 4541-4542.
21. The stereochemistry of all products was proven rigorously. The details are provided as Supporting Information.
22. For a review of five-membered-ring conformational analysis, see: Fuchs, B. Top. Stereochem. 1978, 10, 1-94.
23. Denmark, S. E.; Almstead, N. G. J. Org. Chem. 1994, 59, 5130-5132.
24. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley: New York, 1994; p 697.
25. Reetz, M. T.; Kesseler, K.; Jung, A. Tetrahedron Lett. 1984, 25, 729-732.