The application of the Shapiro reaction to the stereoselective synthesis of E-trisubstituted olefins for cation-olefin cyclization by three component coupling

Tetrahedron Letters

Volumn 38, Issue 52, 1997, Pages 8915-8918

  Corey, E J ^a   Lee, Jaemoon ^a   Roberts, Bryan E ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE;

ARTICLE; CONTROLLED STUDY; CYCLIZATION; DRUG SYNTHESIS; STEREOCHEMISTRY;

EID: 0030778029     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10424-5     Document Type: Article

References (21)

1. Corey, E. J.; Yi, K. Y.; Matsuda, S. P. T. Tetrahedron Lett. 1992, 33, 2319.
2. Corey, E. J.; Noe, M. C.; Shieh, W.-C. Tetrahedron Lett. 1993, 34, 5995.
3. Corey, E. J.; Noe, M. C.; Lin, S. Tetrahedron Lett. 1995, 36, 8741.
4. Corey, E. J.; Lee, J. J. Am. Chem. Soc. 1993, 115, 8873.
5. Corey, E. J.; Lee, J.; Liu, D. R. Tetrahedron Lett. 1994, 35, 9149.
6. Corey, E. J.; Lin, S. J. Am. Chem. Soc. 1996, 118, 8765.
7. Corey, E. J.; Liu, K. J. Am. Chem. Soc. submitted.
8. Corey, E. J.; Luo, G.; Lin, L. S. J. Am. Chem. Soc. in press.
9. Corey, E. J.; Lin, S.; Luo, G. Tetrahedron Lett. 1997, 38, 5771.
10. See: Shapiro, R. H. Org. React. 1976, 23, 405.
11. Corey, E. J.; Dittami, J. P. J. Am. Chem. Soc. 1985, 107, 256.
12. For a summary of the basic work in this area see: (a) Adlington, R. M.; Barrett, A. G. M. Acc. Chem. Res. 1983, 16, 55.
13. (b) J. Chem. Soc. Perkin Trans. I, 1981, 2848.
14. Deprotonation of a trisyl hydrazone nitrogen monoanion generally occurs at the α-carbon syn to the N-trisyl group. For information on the syn dianion effect, see: (a) Shapiro, R. H.; Heath, M. J. J. Am. Chem. Soc. 1967, 89, 5734.
15. (b) Shapiro, R. H. ref. 10.
16. Although n-BuLi is sufficient to effect deprotonation at a primary α-carbon, as in 1, a stronger base (TMEDA-n-BuLi or sec-BuLi) is required to satisfactorily deprotonate at a secondary α-carbon such as in 2. See: Chamberlin, A. R.; Stemke, J. E.; Bond, F. T. J. Org. Chem. 1978, 43, 147.
17. The cuprate is necessary for successful coupling of the vinyl anion with an alkyl iodide. In the absence of a copper source, lithium-halogen exchange followed by homocoupling predominates. For information regarding lithium 2-thienylcyanocuprate, see: Lipshutz, B. H.; Koemer, M.; Parker, D. A. Tetrahedron Lett. 1987, 28, 945.
18. +H: 267.2324 found 267.2335.
19. Four equivalents of 2,3-dibromopropene were used. Due to the greater reactivity of the allyl bromide, significant coupling of 2,3-dibromopropene with thienylcopper occurred.
20. Use of the tert-butyldimethylsilyl derivative leads to facile decomposition.
21. This research was supported by the National Science Foundation and the National Institutes of Health.