Stereochemistry at Carbon in Cleavage of the Carbon-Silicon Bond in exo- and endo-2-NorbornyIpentafluorosilicates by Various Brominating Agents

Journal of the American Chemical Society

Volumn 102, Issue 9, 1980, Pages 3267-3269

  Tamao, Kohei ^a   Yoshida, Jun ichi ^a   Murata, Masao ^a   Kumada, Makoto ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0642365530     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00529a074     Document Type: Letter

References (32)

1. Organofluorosilicates in Organic Synthesis. 9. For part 8, seeTamao, K.; Kakui, T.; Kumada, M. Tetrahedron Lett. 1980, 111.
2. For example: (a) Matteson, D. S. “Organometallic Reaction Mechanisms”; Academic Press: New York, 1974.
3. Kochi, J. K. “Organometallic Mechanisms and Catalysis”; Academic Press: New York, 1978.
4. Johnson, M. D. Acc. Chem. Res. 1978, 11, 57.
5. Reutov, O. A. Tetrahedron 1978, 34, 2827.
6. Jemmis, E. D.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1979, 101, 527.
7. Slack, D. A.; Baird, M. C. J. Am. Chem. Soc. 1976, 98, 5539.
8. Bock, P. L.; Boschetto, D. J.; Rasmussen, J. R.; Demers, J. P.; Whitesides, G. M. J. Am. Chem. Soc. 1974, 96, 2814.
9. Flood, T. C.; DiSanti, F. J. J. Chem. Soc., Chem. Commun. 1975, 18.
10. Flood, T. C.; Miles, D. L. J. Organomet. Chem. 1977, 127, 33.
11. Attig, T. G.; Teller, R. G.; Wu, S.-M.; Bau, R.; Wojcicki, A. J. Am. Chem. Soc. 1979, 101, 619.
12. It has been shown that the base-catalyzed intramolecular rearrangement of a-silylbenzyl alcohols to silyl ethers proceeds with inversion at carbon: (a) Biernbaum, M. S.; Mosher, H. S. J. Am. Chem. Soc. 1971, 93, 6221.
13. Brook, A. G.; Pascoe, J. D. J. Am. Chem. Soc. 1971, 93, 6224. Brominolysis of the aryl-silicon bond has been found to proceed with inversion of configuration at silicon
14. Eaborn, C.; Steward, O. W. J. Chem. Soc. 1965, 521.
15. Mueller, R. Organomet. Chem. Rev. 1966, 1, 359.
16. Tamao, K.; Yoshida, J.; Takahashi, M.; Yamamoto, H.; Kakui, T.; Matsumoto, H.; Kurita, A.; Kumada, M. J. Am. Chem. Soc. 1978, 100, 290.
17. Yoshida, J.; Tamao, K.; Kurita, A.; Kumada, M. Tetrahedron Lett. 1978, 1809.
18. Mueller, R.; Dathe, C. Z. Anorg. Allgem. Chem. 1965, 341, 49.
19. Satisfactory analytical data (C, H. F) were obtained.
20. Kuivila, H. G.; Warner, C. R. J. Org. Chem. 1964, 29, 2845.
21. Cunico, R. F. J. Org. Chem. 1971, 36, 929.
22. In the course of our study on organofluorosilicates, we have found that copper(ll) fluoride is an efficient fluorinating agent of chlorosilanes to give fluorosilanes. Details will be reported elsewhere shortly.
23. Applequist, D. E.; Chmurny, G. N. J. Am. Chem. Soc. 1967, 89, 875.
24. We call attention to the ready epimerization of bromide 2 on analytical and preparative GLC. In the early stage of this work, we encountered this trouble, even though the literature described the analysis and the purification by GLC of this compound.15,17
25. Brown, H. C.; Lane, C. F. Chem. Commun. 1971, 521.
26. Radical chain mechanisms (cf. ref 6a) are also possible. Mechanistic details will be discussed in the full paper. We thank one of the referees for valuable suggestions of the mechanism.
27. Bartlett, P. D.; Fickes, G. N.; Haupt, F. C.; Helgeson, R. Acc. Chem. Res. 1970, 3, 177, and references cited therein.
28. Interestingly, similar stereochemical phenomena have been observed for the conversion of 2-norbornanol into 2-norbornyl bromide by triphenyl-phosphine dibromide: Schaefer, J. P.; Weinberg, D. S. J. Org. Chem. 1965, 30, 2635, 2639.
29. Yoshida, J.; Tamao, K.; Kumada, M.; Kawamura, T. J. Am. Chem. Soc., following paper in this issue.
30. For stereochemical aspects see: (a) Budnik, R. A.; Kochi, J. K. J. Organomet. Chem. 1976, 116, C3.
31. Lane, C. F. J. Organomet. Chem. 1971, 31, 421.
32. Previous methods are of low order of streoselectivity and require the hydrolytic decomposition of the exo isomer: Reference 15 and Roberts, J. D.; Bennett, W.; Armstrong, R. J. Am. Chem. Soc. 1950, 72, 3329.