Olefin inversion: Stereospecific olefin synthesis from Vicinal alkoxyiodoalkanes with butyllithium by an E2 Syn mechanism

Journal of Organic Chemistry

Volumn 61, Issue 20, 1996, Pages 6770-6771

  Maeda, Katsuya ^a   Shinokubo, Hiroshi ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001354730     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961543n     Document Type: Article

References (27)

1. The Chemistry of Alkenes; Patai, S., Ed.; Interscience: New York, 1964. The Chemistry of Alkenes; Zabicky, J., Ed.; Interscience: New York, 1968; Vol. 2.
2. The Chemistry of Alkenes; Patai, S., Ed.; Interscience: New York, 1964. The Chemistry of Alkenes; Zabicky, J., Ed.; Interscience: New York, 1968; Vol. 2.
3. Krebs, A.; Swienty-Busch, J. Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 6, Chapter 5.1, pp 949-974. Kocienski, P. Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 6, Chapter 5.2, pp 975-1010.
4. Krebs, A.; Swienty-Busch, J. Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 6, Chapter 5.1, pp 949-974. Kocienski, P. Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991; Vol. 6, Chapter 5.2, pp 975-1010.
5. Sonnet, P. E. Tetrahedron 1980, 36, 557 and references cited therein. cis-Chlorotelluration-trans-dechlorotelluration: Bäckvall, J.-E.; Engman, L. Tetrahedron Lett. 1981, 22, 1919. vic-Bromohydrin trifluoroacetate with NaI: Sonnet, P. E. J. Org. Chem. 1980, 45, 154. vic-Bromochloride with NaI: Jie, M. S. F. L. K.; Chan, M. F. J. Am. Oil Chem. Soc. 1985, 62, 109.
6. Sonnet, P. E. Tetrahedron 1980, 36, 557 and references cited therein. cis-Chlorotelluration-trans-dechlorotelluration: Bäckvall, J.-E.; Engman, L. Tetrahedron Lett. 1981, 22, 1919. vic-Bromohydrin trifluoroacetate with NaI: Sonnet, P. E. J. Org. Chem. 1980, 45, 154. vic-Bromochloride with NaI: Jie, M. S. F. L. K.; Chan, M. F. J. Am. Oil Chem. Soc. 1985, 62, 109.
7. Sonnet, P. E. Tetrahedron 1980, 36, 557 and references cited therein. cis-Chlorotelluration-trans-dechlorotelluration: Bäckvall, J.-E.; Engman, L. Tetrahedron Lett. 1981, 22, 1919. vic-Bromohydrin trifluoroacetate with NaI: Sonnet, P. E. J. Org. Chem. 1980, 45, 154. vic-Bromochloride with NaI: Jie, M. S. F. L. K.; Chan, M. F. J. Am. Oil Chem. Soc. 1985, 62, 109.
8. Sonnet, P. E. Tetrahedron 1980, 36, 557 and references cited therein. cis-Chlorotelluration-trans-dechlorotelluration: Bäckvall, J.-E.; Engman, L. Tetrahedron Lett. 1981, 22, 1919. vic-Bromohydrin trifluoroacetate with NaI: Sonnet, P. E. J. Org. Chem. 1980, 45, 154. vic-Bromochloride with NaI: Jie, M. S. F. L. K.; Chan, M. F. J. Am. Oil Chem. Soc. 1985, 62, 109.
9. Bach, R. D.; Badger, R. C.; Lang, T. J. J. Am. Chem. Soc. 1979, 101, 2845. McLennan, D. J.; Lim, G. C. Aust. J. Chem. 1983, 36, 1821. Ogawa, S.; Takagaki, T. J. Org. Chem. 1985, 50, 2356.
10. Bach, R. D.; Badger, R. C.; Lang, T. J. J. Am. Chem. Soc. 1979, 101, 2845. McLennan, D. J.; Lim, G. C. Aust. J. Chem. 1983, 36, 1821. Ogawa, S.; Takagaki, T. J. Org. Chem. 1985, 50, 2356.
11. Bach, R. D.; Badger, R. C.; Lang, T. J. J. Am. Chem. Soc. 1979, 101, 2845. McLennan, D. J.; Lim, G. C. Aust. J. Chem. 1983, 36, 1821. Ogawa, S.; Takagaki, T. J. Org. Chem. 1985, 50, 2356.
12. Cis E2 reaction of trans-2-arylcyclopentyl tosylate: Depuy, C. H.; Morris, G. F.; Smith, J. S.; Smat, R. J. J. Am. Chem. Soc. 1965, 87, 2421. Cis-1,2-elimination of 1,2-dibromo compounds with bis(trimethylsilyl)mercury: Bennett, S. W.; Eaborn, C.; Jackson, R. A.; Walsingham, R. W. J. Organomet. Chem. 1971, 27, 195.
13. Cis E2 reaction of trans-2-arylcyclopentyl tosylate: Depuy, C. H.; Morris, G. F.; Smith, J. S.; Smat, R. J. J. Am. Chem. Soc. 1965, 87, 2421. Cis-1,2-elimination of 1,2-dibromo compounds with bis(trimethylsilyl)mercury: Bennett, S. W.; Eaborn, C.; Jackson, R. A.; Walsingham, R. W. J. Organomet. Chem. 1971, 27, 195.
14. Nicolaou, K. C.; Duggan, M. E.; Ladduwahatty, T. Tetrahedron Lett. 1984, 25, 2069. Wender, P. A.; Keenan, R. M.; Lee, H. Y. J. Am. Chem. Soc. 1987, 109, 4390. Rao, A. V. R.; Reddy, E. R.; Joshi, B. V.; Yadav, J. S. Tetrahedron Lett. 1987, 28, 6497. Ireland, R. E.; Häbich, D.; Norbech, D. W. J. Am. Chem. Soc. 1985, 107, 3271. The stereochemical outcome has not been discussed in the foregoing literature.
15. Nicolaou, K. C.; Duggan, M. E.; Ladduwahatty, T. Tetrahedron Lett. 1984, 25, 2069. Wender, P. A.; Keenan, R. M.; Lee, H. Y. J. Am. Chem. Soc. 1987, 109, 4390. Rao, A. V. R.; Reddy, E. R.; Joshi, B. V.; Yadav, J. S. Tetrahedron Lett. 1987, 28, 6497. Ireland, R. E.; Häbich, D.; Norbech, D. W. J. Am. Chem. Soc. 1985, 107, 3271. The stereochemical outcome has not been discussed in the foregoing literature.
16. Nicolaou, K. C.; Duggan, M. E.; Ladduwahatty, T. Tetrahedron Lett. 1984, 25, 2069. Wender, P. A.; Keenan, R. M.; Lee, H. Y. J. Am. Chem. Soc. 1987, 109, 4390. Rao, A. V. R.; Reddy, E. R.; Joshi, B. V.; Yadav, J. S. Tetrahedron Lett. 1987, 28, 6497. Ireland, R. E.; Häbich, D.; Norbech, D. W. J. Am. Chem. Soc. 1985, 107, 3271. The stereochemical outcome has not been discussed in the foregoing literature.
17. Nicolaou, K. C.; Duggan, M. E.; Ladduwahatty, T. Tetrahedron Lett. 1984, 25, 2069. Wender, P. A.; Keenan, R. M.; Lee, H. Y. J. Am. Chem. Soc. 1987, 109, 4390. Rao, A. V. R.; Reddy, E. R.; Joshi, B. V.; Yadav, J. S. Tetrahedron Lett. 1987, 28, 6497. Ireland, R. E.; Häbich, D.; Norbech, D. W. J. Am. Chem. Soc. 1985, 107, 3271. The stereochemical outcome has not been discussed in the foregoing literature.
18. The stereoselective conversion of iodo acetals into alkenyl ethers has been reported. Maeda, K.; Shinokubo, H.; Oshima, K.; Utimoto, K. J. Org. Chem. 1996, 61, 2262.
19. Cambie, R. C.; Noall, W. I.; Potter, G. J.; Rutledge, P. S.; Woodgate, P. D. J. Chem. Soc., Perkin Trans, 1 1977, 226.
20. 11 was also obtained in 5-10% yield.
21. Stereospecific β-elimination of conformationally rigid bromo ethers with Na or Zn has been reported in the synthesis of natural products. Schlessinger, R. H.; Nugent, R. A. J. Am. Chem. Soc. 1982, 104, 1116. Kato, T.; Aoki, M.; Uyehara, T. J. Org. Chem. 1987, 52, 1803.
22. Stereospecific β-elimination of conformationally rigid bromo ethers with Na or Zn has been reported in the synthesis of natural products. Schlessinger, R. H.; Nugent, R. A. J. Am. Chem. Soc. 1982, 104, 1116. Kato, T.; Aoki, M.; Uyehara, T. J. Org. Chem. 1987, 52, 1803.
23. 2Zn provided the same isomeric mixture of 6-dodecene (E/Z = 91/9).
24. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356. Stanetty, P.; Krumpak, B.; Rodler, I. K. J. Chem. Res., Miniprint 1995, 2110. Halogen-metal exchange followed by syn elimination of LiOMe might be an alternative mechanism. However, this proposed mechanism could be negated by the fact that the reaction of 1a and 1b with s-BuLi and t-BuLi gave stereochemical results different from those obtained in the reaction with n-BuLi.
25. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356. Stanetty, P.; Krumpak, B.; Rodler, I. K. J. Chem. Res., Miniprint 1995, 2110. Halogen-metal exchange followed by syn elimination of LiOMe might be an alternative mechanism. However, this proposed mechanism could be negated by the fact that the reaction of 1a and 1b with s-BuLi and t-BuLi gave stereochemical results different from those obtained in the reaction with n-BuLi.
26. A radical intermediate might be involved in the course of the reaction. Single electron transfer from Grignard reagent into iodoalkanes followed by departure of iodide would produce the carbon radical. Second single electron transfer would provide a carbanion that collapses to alkene along with the elimination of the methoxide ion.
27. 2/MeOH and butylmagnesium bromide. For instance, trans-cyclododecene (>99/<1) was obtained in 80% overall yield from a commercially available (Nacalai tesque, Inc.) cis- and trans-cyclododecene (34/66). Moreover, trans-cyclododecene could be converted into cis-isomer (cis / trans = > 99/ < 1) in 75% overall yield by methoxyiodination and subsequent treatment with butyllithium in hexane-ether.