Abstract
New rhodium-catalyzed amination reactions of arylacetylenes and cyclohexen-1-ylacetylene in the presence of strong bases with the use of carbon dioxide as an auxiliary are described. Secondary amines attack the terminal carbon atom of the triple bond followed by protonation of the adjacent carbon atom. Alternatively, the reaction can proceed further with the addition of the second alkyne molecule. The conditions for the selective synthesis of enamines (up to 87% yield) or α-substituted propynylamines (up to 86% yield) are reported.
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References
The Chemistry of Enamines, Ed. Z. Rappoport, Wiley, New York, 1994.
E. Winterfeldt,Angew. Chem., Int. Ed. Engl., 1967,6, 423.
O. Cervinca, inThe Chemistry of Enamines, Part 1, Ed. Z. Rappoport, Wiley, New York, 1994, 467; (b) D. M. Barlex, R. D. W. Kemmitt, and G. W. Littlecott,J. Organomet. Chem., 1972,43, 225; P. C. Kong and T. Theophanides,Inorg. Chim. Acta, 1973,7, 299; (c) J. Barluenga, F. Aznar, R. Liz, and R. Rodes,J. Chem. Soc., Perkin Trans. I, 1983, 1087; J. Barluenga and F. Aznar,Synthesis, 1975, 704.
C. Gardener, V. Kerrigan, J. D. Rose, and B. C. L. Weedan,J. Chem. Soc., 1949, 780; (b) J. D. Rose and R. A. Gale,J. Chem. Soc., 1949, 792; (c) K. C. Brannock, R. D. Burpitt, and J. G. Thweatt,J. Org. Chem., 1963,28, 1462.
K. Utimoto, H. Miwa, and H. Nozaki,Tetrahedron Lett., 1981,22, 4277.
J. Schniedermeier and H. -J. Haupt,J. Organomet. Chem., 1996,506, 41.
Critical Stability Constants,1, 2, Eds., R. M. Smith and A. E. Martell, Plenum Press, New York, 1975, 72.
R. Schwesinger,Chimia, 1985,39, 269; R. Schwesinger, J. Willaredt, H. Schlemper, M. Keller, D. Schmitt, and H. Fritz,Chem. Ber., 1994,127, 2435.
C. Bruneau and P. H. Dixneuf,J. Mol. Catal., 1992,74, 97 (and references therein).
M. Costa, G. P. Chiusoli, and M. Rizzardi,Chem. Commun., 1966, 1699.
J. A. Osborn and G. Wilkinson,Inorg. Synth., John Wiley, New York, 1990,28, 77; (b) R. Cramer,Inorg Synth., John Wiley, New York, 1990,28, 86.
T. G. Schenck, J. M. Downes, C. R. C. Milne, P. B. Mackenzie, H. Boucher, J. Whelan, and B. Bosnich,Inorg. Chem., 1985,24, 2334.
U. Schuchardt, R. M. Vargas, and G. Gelbard,J. Mol. Catal., 1995,99, 65.
J. E. Cragg, R. B. Herbert, F. B. Jackson, C. J. Moody, and I. T. Nicolson,J. Chem. Soc., Perkin Trans. 1, 1982, 2477.
R. Dulou, E. Elkik, and A. Veillard,Bull. Soc. Chim. Fr., 1960, 967.
P. L. Southwik and J. R. Kirchner,J. Org. Chem., 1962,27, 3305.
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Dipartimento di Chimica Organica e Industriale dell'Università, Viale delle Scienze, I-43100 Parma, Italia.
Dipartimento di Chimica, Università della Calabria, Arcavacata di Rende, I-80036 Cosenza, Italia.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 966–970, May, 1998.
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Costa, M., Chiusoli, G.P., Gaetti, R. et al. Amination of aryl- and vinylacetylenic compounds catalyzed by rhodium(I) complexes. Russ Chem Bull 47, 936–940 (1998). https://doi.org/10.1007/BF02498165
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DOI: https://doi.org/10.1007/BF02498165