The reductive coupling of tertiary amides to give enediamines using PhMe₂SiLi

Abstract

PhMe₂SiLi reacts with tertiary amides to give enediamines, which can be isolated in good yield when the α-carbon is branched; the enediamines can be hydrolysed more or less easily to α-amino ketones, isomerised from Z to E, oxidised to dienediamines and isomerised to amino enamines.

References

1. M. V. George, D. J. Peterson and H. Gilman, J. Am. Chem. Soc., 1960, 82, 403; A. S. Guram and G. A. Krafft, in Encyclopaedia of Reagents for Organic Synthesis, ed. L. A. Paquette, Wiley, Chichester, 1995, p. 2113; I. Fleming, in Synthetic Methods of Organometallic and Inorganic Chemistry (Hermann/Brauer), ed. N. Auner and U. Klingebiel, Georg Thieme, Stuttgart, 1996, vol. 2, p. 167.
2. B. F. Bonini, F. Busi, R. C. de Laet, G. Mazzanti, J.-W. J. F. Thuring, P. Zani and B. Zwanenburg, J. Chem. Soc., Perkin Trans. 1, 1993, 1011; B. F. Bonini, M. Comes-Franchini, G. Mazzanti, U. Passamonti, A. Ricci and P. Zani, Synthesis, 1995, 92 For some related reactions see also: J. Kang, J. H. Lee, K. S. Kim, J. U. Jeong and C. Pyun, Tetrahedron Lett., 1987, 28, 3261; A. G. Brook, A. Baumegger and A. J. Lough, Organometallics, 1992, 11, 310; K. Yamamoto, A. Hayashi, S. Suzuki and J. Tsuji, Organometallics, 1987, 6, 974; A. Ricci, A. Degl'Innocenti, S. Chimichi, M. Fiorenza, G. Rossini and H. J. Bestmann, J. Org. Chem., 1985, 50, 130; F. Jin, B. Jiang and Y. Xu, Tetrahedron Lett., 1992, 33, 1221; M. Nakada, S. Nakamura, S. Kobayashi and M. Ohno, Tetrahedron Lett., 1991, 32, 4929; P. Bourgeois, J. Dunoguès and N. Duffaut, J. Organomet. Chem., 1974, 80, C25; J.-P. Picard, R. Calas, J. Dunoguès, N. Duffaut, J. Gerval and P. Lapouyade, J. Org. Chem., 1979, 44, 420; P. Bourgeois, J. Organomet. Chem., 1974, 76, C1; N. Kise, H. Kaneko, N. Uemoto and J. Yoshida, Tetrahedron Lett., 1995, 36, 8839.
3. I. Fleming, M. Solay and F. Stolwijk, J. Organomet. Chem., 1996, 521, 121.
4. I. Fleming and U. Ghosh, J. Chem. Soc., Perkin Trans. 1, 1994, 257.
5. S. Nahm and S. M. Weinreb, Tetrahedron Lett., 1981, 22, 3815.
6. D. Lee, Ph.D., Thesis, Cambridge, 1997.
7. D. A. Bravozhitivitovsk, S. D. Pigarev, I. D. Kalikhman, O. A. Vyazankina and N. S. Vyazankin, J. Organomet. Chem., 1983, 114, 51.
8. P. R. Raithby, H. R. Powell and C. Wilson, unpublished work, Cambridge, 1994.
9. K. C. Brannock, A. Bell, R. D. Burpitt and C. A. Kelly, J. Org. Chem., 1964, 29, 801; K. C. Brannock, R. D. Burpitt, V. W. Goodlett and J. G. Thweatt, J. Org. Chem., 1964, 29, 813; I. Fleming and J. Harley-Mason, J. Chem. Soc., 1964, 2165.
10. A. Ogawa, N. Takami, M. Sekiguchi, I. Ryu, N. Kambe and N. Sonoda, J. Am. Chem. Soc., 1992, 114, 8729.
11. A. Ogawa, T. Nanke, N. Takami, M. Sekiguchi, N. Kambe and N. Sonoda, Appl. Organomet. Chem., 1995, 9, 461.