Wurtz-type coupling reaction of pseudo-pentacoordinate halodisilanes using magnesium: Enhanced reactivity of the silicon-halogen bond by intramolecular amine-coordination to silicon

Chemistry Letters

Volumn , Issue 4, 1999, Pages 335-336

  Tamao, Kohei ^a   Asahara, Masahiro ^a   Saeki, Tomoyuki ^a   Toshimitsu, Akio ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0033245695     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1999.335     Document Type: Article

References (34)

1. a) R. C. Miller and J. Michl, Chem. Rev., 89, 1359 (1989).
2. b) R. West, in "The Chemistry of Organic Silicon Compounds," ed by S. Patai and Z. Rappoport, Wiley, Chichester, England (1989), p. 1207.
3. a) G. Sawitzki and H. G. von Schnering, Chem. Ber., 109, 3728 (1976).
4. b) D. Kummer, A. Balkir, and H. Köster, J. Organomet. Chem., 178, 29 (1979).
5. c) U. Schubelt, M. Wiener, and F. H. Köhler, Chem. Ber., 112, 708 (1979).
6. d) J. Grobe, Z. Naturforsch., B, 39, 341 (1984).
7. e) M. Kira, K. Sato, C. Kabuto, and H. Sakurai, J. Am. Chem. Soc., 111, 3747 (1989).
8. f) K. Tamao, Y. Tarao, Y. Nakagawa, K. Nagata, and Y. Ito, Organometallics, 12, 1113 (1993).
9. g) K. Tamao, K. Nagata, M. Asahara, A. Kawachi, Y. Ito, and M. Shiro, J. Am. Chem. Soc., 117, 11592 (1995).
10. h) K. Tamao, M. Asahara, and A. Kawachi, J. Organomet. Chem., 521, 325 (1996).
11. i) K. Tamao, M. Asahara, G.-R. Sun, and A. Kawachi, J. Organomet. Chem., in press.
12. a) J. Belzner, J. Organomet. Chem., 430, C51 (1992).
13. b) J. Belzner, H. Ihmels, B. O. Kneisel, R. O. Gould, and R. Herbst-Irmer, Organometallics, 14, 305 (1995).
14. c) J. Belzner, U. Dehnert, H. Ihmels, M. Hübner, P. Müller, and I. Usón, Chem. Eur. J., 4, 852 (1998).
15. The formation of linear oligomers from base-coordinated silylenes has also been suggested without successful characterization; R. Corriu, G. Lanneau, C. Priou, F. Soulairol, N. Auner, R. Probst, R. Conlin, and C. Tan, J. Organomet. Chem., 466, 55 (1994).
16. Y. Hatanaka, I. El-Sayed, S. Shimada, and M. Tanaka, The 45th Symposium on Organometallic Chemistry, Japan, Tokyo, September, 1998, Abstr., p. 8; and private communications.
17. In the reaction of 1a with sodium instead of magnesium in THF, the starting material was recovered at 15 °C and a complex mixture containing no coupling product 2 was formed under reflux, thus indicating the importance of the choice of reducing reagent.
18. max = 110.6°.
19. max = 120.2°.
20. 10
21. H. Bock, Z. Havlas, and V. Krenzel, Angew. Chem. Int. Ed. Engl., 37, 3163 (1998).
22. A. Bondi, J. Phys. Chem., 68, 441 (1964).
23. a) R. J. P. Corriu and J. C. Young, in "The Chemistry of Organic Silicon Compounds," ed by S. Patai and Z. Rappoport, Wiley, Chichester, England (1989), p. 1241.
24. b) C. Chuit, R. J. P. Corriu, C. Rey, and J. C. Young, Chem. Rev., 93, 1371 (1993).
25. a are as follows: dl-2; Sil, 13%; Si3*, 19%; meso-2; Si2, 11%.
26. K. Tamao, T. Hayashi, and Y. Ito, Organometallics, 11, 2099 (1992).
27. W. S. Sheldrick, in "The Chemistry of Organic Silicon Compounds," ed by S. Patai and Z. Rappoport, Wiley, Chichester, England (1989), p. 227.
28. We are grateful to both referees for the suggestion of this point, of which we were not aware.
29. Terminal silicon atoms resonate in the same region as follows: -19.1 ppm for meso-2, -18.4 ppm for dl-2, -17.1 ppm for meso-4, and -16.7 ppm for dl-4.
30. a)St. N. Tandura, N. V. Alekseev, and M. G. Voronkov, Top. Curr. Chem., 131, 99 (1986).
31. b) D. Kost and I. Kalikhman, in "The Chemistry of Organic Silicon Compounds," ed by Z. Rappoport and Y. Apeloig, Wiley, Chichester, England (1998), Vol. 2, p. 1339.
32. F. Care, G. Cerveau, C. Chuit, R. J. P. Corriu, N. K. Nayyar, and C. Reye, Organometallics, 9, 1989 (1990).
33. K. Tamao, M. Asahara, A. Kawachi, and A. Toshimitsu, manuscript under preparation.
34. C. L. Smith and R. Gooden, J. Organomet. Chem., 81, 33 (1974).