Induction of Asymmetry by a Remote Chiral Center in the Amide Acetal Claisen Rearrangement

Journal of the American Chemical Society

Volumn 109, Issue 22, 1987, Pages 6716-6719

  Welch, John T ^a   Eswarakrishnan, Seetha ^a  

^a STATE UNIVERSITY OF NEW YORK   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000822844     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00256a026     Document Type: Article

References (16)

1. Welch. J. T.; Eswarakrishnan, S. J. Org. Chem. 1985, 50. 5909–5910.
2. Stereocontrol where the newly created centers bear a specific relationship to the preexisting chiral center is termed relative asymmetric induction; when the newly created centers bear a relationship only between themselves, it is termed internal asymmetric induction. Bartlett, P. A. Tetrahedron 1980, 36, 2–73.
3. Bennet, G. B. Synthesis 1977, 589–606. Ziegler, R. E. Acc. Chem. Res. 1977, 10, 227–232. Hill, R. K. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic: New York, 1984; Vol. 3, Chapter 8. Fujisawa, T. Tajima, K.; Sato, T. Chem. Lett. 1984, 1669–1672. Fujisawa, T.; Tajima, K.; Ho, M.; Sato, T. Chem. Lett. 1984, 1169–1172, Ireland, R. E.: Varney, M. D. J. Am. Chem. Soc. 1984, 106, 3668–3670.
4. Morrow, D. F.; Culbertson, T. P.; Hofer, R. M. J. Org. Chem. 1967, 32, 361–369. Mikami, K.; Kawamoto, K.; Nakai, T. Chem. Lett. 1985. 115–118.
5. Church, R. F.; Ireland, R. E.; Marshall, J. A. J. Org. Chem. 1962, 27, 1118–1125. Church, R. F.; Ireland, R. E. J. Org. Chem. 1963, 28, 17–23.
6. Ziegler. F. E.; Thottathil, J. K. Tetrahedron Lett. 1982. 23. 3531–3534.
7. Kurth, M. J.; Decker, O. H. W. Tetrahedron Lett. 1983, 24, 4535–4538. Kurth, M. J.; Decker, O. H. W.; Hope, H.; Yanuck, M. D. J. Am. Chem. Soc. 1985, 107, 443–448.
8. Kurth, M. J.; Yu, C. M. J. Org. Chem. 1985, 50, 1840–1845. Fujisawa, T.: Taiima, K.: Ito. M.; Sato. T. Chem. Lett. 1984, 1169–1172.
9. Mikami, K.; Fujimoto, K.; Kasuga, T.; Nakai, T. Tetrahedron Lett. 1984, 25, 6011–6014. Mikami, K.; Takahashi, O.; Kasuga, T.; Nakai, T. Chem. Lett. 1985, 1729–1732. Kallmerton, J.; Gould, T. J. J. Org. Chem. 1986. 51. 1152–1155.
10. Cha, J. K.; Lewis, S. C. Tetrahedron Lett. 1984, 25, 5263–5266.
11. Takacs, J. M. Ph.D. Dissertation, California Institute of Technology, Pasadena. CA. 1981.
12. Amides from the rearrangement of lb, 3b/4b, and 5b/6b were formed in a ratio of 2:1 from the reaction of the E alcohol and in a ratio of 1:3 from the Z alcohol. For reactions of the E alcohol, 3b and 4b were formed as a 2.3:1 mixture, whereas 5b and 6b were formed from the Z alcohol as a 1.9:1 mixture. Amides from the rearrangement of lc, 3c/4c, and 5c/6c were formed in a ratio of 2:1 for the reaction of the E alcohol and in a ratio of 1:2.8 from the Z alcohol. For reactions of the E alcohol, 3 and 4 were formed as a 2.2:1 mixture, whereas 5 and 6 were formed from the Z alcohol as a 1.8:1 mixture.
13. Pedersen, B. S.; Scheiby, S.; Clausen, K.; Lawesson, SO. Bull. Soc. Chim. Belg. 1978, 87, 293–297.
14. Birch, S. F.: McAllan, D. R. J. Chem. Soc. 1951, 2556–2563.
15. Tamaru, Y.; Furukawa, Y.; Mizutani, M.; Kitao, O.; Yoshida, Z. J. Org. Chem. 1983, 48, 3631–3639. Tamaru, Y.; Harada, T.; Yoshida, Z. J. Am. Chem. Soc. 1980, 102, 2392–2398.
16. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923–2925.