Tandem insertion of allenyl carbenoids and aldehydes into zirconacycles: an unexpected cyclisation

Abstract

Allenyl carbenoids (3-chloro-1-lithioalk-1-ynes) insert into zirconacyclopentanes and zirconacyclopentenes to afford cyclic η³-allenyl/prop-2-ynyl zirconocene complexes which give allenyl, alkynyl or cyclised-alcohol products on addition of aldehydes activated with boron trifluoride–diethyl ether.

References

1. E.-I. Negishi and T. Takahashi, Acc. Chem. Res., 1994, 27, 124; R. D. Broene and S. L. Buchwald, Science, 1993, 261, 1696; E. Negishi, in Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon Press, Oxford, 1991, vol. 5, p. 1163; S. L. Buchwald and R. D. Broene, in Comprehensive Organometallic Chemistry II, ed. E. W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon, Oxford, UK, 1995, Vol. 12; p. 771 and R. D. Broene, p. 323.
2. D. Swanson, C. Rousset, E. Negishi, T. Takahashi, T. Seki, M. Saburi and Y. Uchida, J. Org. Chem., 1989, 54, 3521; E. Negishi, S. J. Holmes, J. M. Tour, J. A. Miller, F. E. Cederbaum, D. R. Swanson and T. Takahashi, J. Am. Chem. Soc., 1989, 111, 3336.
3. J. M. Davis, R. J. Whitby and A. Jaxa-Chamiec, Tetrahedron Lett., 1992, 33, 5655; G. D. Probert, R. J. Whitby and S. J. Coote, Tetrahedron Lett., 1995, 36, 4113; K. Aoyagi, K. Kasai, D. Y. Kondakov, R. Hara, N. Suzuki and T. Takahashi, Inorg. Chim. Acta, 1994, 220, 319.
4. C. Coperet, E. I. Negishi, Z. F. Xi and T. Takahashi, Tetrahedron Lett., 1994, 35, 695.
5. T. Takahashi, M. Kotora and Z. F. Xi, J. Chem. Soc., Chem. Commun., 1995, 1503; T. Takahashi, R. Hara, Y. Nishihara and M. Kotora, J. Am. Chem. Soc., 1996, 118, 5154; K. Kasai, M. Kotora, N. Suzuki and T. Takahashi, J. Chem. Soc., Chem. Commun., 1995, 109; B. H. Lipshutz and M. Segi, Tetrahedron, 1995, 51, 4407.
6. T. Luker and R. J. Whitby, Tetrahedron Lett., 1994, 35, 785, 9465; 1995, 36, 4109; G. J. Gordon and R. J. Whitby, Synlett, 1995, 77.
7. G. J. Gordon and R. J. Whitby, Chem. Commun., 1997, 1045.
8. E. Negishi, F. E. Cederbaum and T. Takahashi, Tetrahedron Lett., 1986, 27, 2829.
9. T. Takahashi, M. Kageyama, V. Denisov, R. Hara and E. Negishi, Tetrahedron Lett., 1993, 34, 687.
10. P. W. Blosser, J. C. Gallucci and A. Wojcicki, J. Am. Chem. Soc., 1993, 115, 2994.
11. A. Wojcicki, New J. Chem., 1994, 18, 61.
12. J. A. Miller and E. Negishi, Israel J. Chem., 1984, 24, 76; A. E. Harms and J. R. Stille, Tetrahedron Lett., 1992, 33, 6565; K. H. Shaughnessy and R. M. Waymouth, J. Am. Chem. Soc., 1995, 117, 5873.