Mechanism of metal-carbenoid insertion into the Si-H bond

Tetrahedron Letters

Volumn 38, Issue 2, 1997, Pages 229-232

  Landais, Yannick ^a   Parra Rapado, Liliana ^a   Planchenault, Denis ^a   Weber, Valéry ^a  

^a UNIVERSITY OF LAUSANNE   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOSILICON DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0031029518     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02285-X     Document Type: Article

References (28)

1. (a) Rijkens, F.; Janssen, M.J.; Drenth, W.; VanDerKerk, G.J.M. J. Organomet. Chem., 1964, 2, 347-356;
2. (b) Watanabe, H.; Kakano, T.; Araki, K.; Matsumoto, H.; Nagai, Y. J. Organomet. Chem., 1974, 69, 389-396;
3. (c)Barnier, J.-P.; Blanco, L. J. Organomet. Chem., 1996, 514, 67-71.
4. Bagheri, V.; Doyle, M.P.; Taunton, J.; Claxton, L.E. J. Org. Chem., 1988, 53, 6158-6160.
5. (a) Andrey, O.; Landais, Y.; Planchenault, D. Tetrahedron Lett., 1993, 34, 2927-2930;
6. (b) Andrey, O.; Landais, Y.; Planchenault, D.; Weber, V. Tetrahedron, 1995, 51, 12083-12096;
7. (c)Landais, Y.; Planchenault, D. Tetrahedron, 1995, 57, 12097-12108;
8. (d)Landais, Y.; Planchenault, D. Tetrahedron Lett., 1994, 35, 4565-4568;
9. (e) Landais, Y.; Planchenault, D.; Weber, V. Tetrahedron Lett., 1994, 35, 9549-9552;
10. (f) Landais, Y.; Planchenault, D. Tetrahedron, 1996, (In press).
11. Seyferth, D.; Damrauer, R.; Mui, J.Y.-P.; Jula, T.F. J. Am. Chem. Soc., 1968, 90, 2944-2948.
12. Doyle, M.P. Recl. Trav. Chim. Pays-Bas, 1991,110, 305-316.
13. Taber, D.F. in Comprehensive Organic Synthesis; Trost, B.M., Fleming, I., Ed.; Pergamon Press: Oxford, U.K. 1991; Vol. 4, pp 1045-1062 and references cited therein.
14. Doyle, M.P.; Westrum, L.J.; Wendelmoed, N.E.W.; See, M.M.; Boone, W.P.; Bagheri, V.; Pearson, M.M. J. Am. Chem. Soc., 1993, 115, 958-964.
15. (a) Wiberg, K.B. Chem. Rev., 1955, 55, 713-743;
16. (b) Westheimer, F.H. Chem. Rev., 1961, 61, 265-273.
17. 2SiD and found that 5b was obtained in 90% yield, with complete incorporation of deuterium.
18. 2O which gave KIE values of 2.57 and 1.7 respectively.
19. Hansch, C.; Leo, A.; Taft, R.W. Chem. Rev., 1991, 91, 165-195.
20. +.
21. Streitwieser, A., Jr. Solvolytic Displacement Reactions; Mc Graw Hill : New-York, 1962, 43.
22. Mayr, H.; Basso, N.; Hagen, G. J. Am. Chem. Soc., 1992,114, 3060-3066 and references cited therein.
23. 3d,f again supporting the occurrence of an early transition state.
24. (a) Wolf, J.R.; Hamaker, C.G.; Djukic, J.-P.; Kodadek, T.; Woo, L.K. J. Am. Chem. Soc., 1995, 117, 9194-9199;
25. (b) Müller, P.; Fernandez, D. Helv. Chim. Acta, 1995, 78, 947-958.
26. 14 A polar mechanism with rate determining formation of silicenium ion was proposed (p=2.46). Such a polar mechanism would imply more charge development at the transition state than that suggested by the LFER studies (Fig.-l) and therefore can be ruled out.
27. Bulugahapitiya, P.; Landais, Y.; Parra-Rapado, L.; Planchenault, D.; Weber, V. J. Org. Chem.(Submitted).
28. 3d The hydrosilylation product observed in this case might be formed through an ionic pathway and not via oxidative addition, as suggested by some recent investigations carried out in our laboratories which will be reported in a forthcoming article.