Methyl exchange on silicon during the addition of methylmagnesium iodide to a cyanohydrin O-silyl ether

Abstract

Reaction of [¹³C]methylmagnesium iodide (99 atom% ¹³C) with cyanohydrin O-trimethylsilyl ether 1, followed by acidic hydrolysis, led to the formation of a methyl ketone derivative 2a that was only partially labelled (60 ± 5 atom% ¹³C); this loss of labelling occurred through a methyl exchange reaction on silicon as shown by the presence on intermediate 2b of [¹³C]methyl groups on silicon (30 atom% ¹³C).

References

1. W. R. Jackson, H. A. Jacobs, G. S. Jayatilake, B. R. Matthews and K. G. Watson, Aust. J. Chem., 1990, 43, 2045.
2. J. R. Luly, C. N. Hsiao, N. BaMaung and J. J. Plattner, J. Org. Chem., 1988, 53, 6109.
3. W. R. Jackson, H. A. Jacobs, B. R. Matthews, G. S. Jayatilake and K. G. Watson, Tetrahedron Lett., 1990, 31, 1447.
4. M. Gill, M. J. Kiefer, D. A. Lally and A. Ten, Aust. J. Chem., 1990, 43, 1497.
5. G. Pattenden, N. A. Pegg and R. W. Kenyon, J. Chem. Soc., Perkin Trans. 1, 1991, 2363.
6. I. Oprean, H. Ciupe, L. Gansca and F. Hodosan, J. Prakt. Chem., 1987, 329, 283.
7. J. P. Lepoittevin, J. Drieghes and A. Goossens, Arch. Dermatol., 1995, 131, 31.
8. M. Matura, J. P. Lepoittevin, C. Arbez-Gindre and A. Goossens, Contact Dermatitis, 1998, 38, 106.
9. M calculated for C₂₆H₄₂O₂S₂Si: 478.24.
10. P. Canonne, G. B. Foscolos and G. Lemay, Tetrahedron Lett., 1980, 21, 155.
11. E. C. Ashby, L. C. Chao and H. M. Neumann, J. Am. Chem. Soc., 1973, 95, 4896.
12. F. Effenberger, B. Gutterer and J. Syed, Tetrahedron: Asymmetry, 1995, 6, 2933.