Zinc(II) complexes of phosphonic acid analogues of aspartic acid and asparagine

Abstract

An analogue of aspartic acid obtained by the replacement of the α-carboxylic group by a phosphonic acid group underwent chemical transformation upon the action of zinc(II) ions under neutral and slightly alkaline conditions yielding, most probably, a cyclic phosphonamidate composed of two ligand molecules. In contrast, an analogue obtained by the replacement of the β-carboxylic group by a phosphonic acid moiety did not undergo such a transformation. In order to determine which structural features are responsible for the observed cyclization a series of aminophosphonic acids was synthesized and their behaviour in zinc(II) solutions studied by means of NMR spectroscopy. Cyclization of 1-aminoalkylphosphonic acids upon the action of zinc(II) ions in neutral and slightly alkaline media seems to be a general property of these acids. The crystal structures of two of the studied compounds were also determined.

References

1. E. Matczak-Jon, B. Kurzak, W. Sawka-Dobrowolska, P. Kafarski and B. Lejczak, J. Chem. Soc., Dalton Trans., 1996, 3455.
2. M. Soroka and P. Mastalerz, Pol. J. Chem., 1976, 50, 661; J. Oleksyszyn, E. Gruszecka, P. Kafarski and P. Mastalerz, Monatsh. Chem., 1982, 113, 1138.
3. (a) M. Soroka, Liebigs Ann. Chem., 1990, 331; (b) M. Soroka, D. Jaworska and M. Szczȩsny, Liebigs Ann. Chem., 1990, 1153.
4. G. Gran, Acta Chem. Scand., 1959, 4, 599.
5. M. Molina, C. Melios, J. O. Tognalli, L. C. Luchiari and M. Jafelicci jun., J. Electroanal. Chem., Interfacial Electrochem., 1979, 105, 237.
6. P. Gans, A. Sabatini and A. Vacca, J. Chem. Soc., Dalton Trans., 1985, 1195.
7. Kuma KM4 software. User's Guide, version 3.1, Kuma Diffraction, Wrocław, 1987.
8. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
9. G. M. Sheldrick, SHELXL 93, Program for the Refinement of Crystal Structures, University of Göttingen, 1993.
10. H. D. Flack, Acta Crystallogr., Sect. A, 1983, 39, 876.
11. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
12. Z. Siatecki and H. Kozłowski, Org. Magn. Reson., 1980, 5, 431; 7, 172.
13. K. G. R. Pachler, Spectrochim. Acta, 1964, 20, 581.
14. T. Kiss, E. Farkas and H. Kozłowski, Inorg. Chim. Acta, 1989, 155, 281.
15. W. Sawka-Dobrowolska, T. Głowiak, Z. Siatecki and M. Soroka, Acta Crystallogr., Sect. C, 1985, 41, 453.
16. F. S. Stephens, R. S. Vagg and P. A. Williams, Acta Crystallogr., Sect. B, 1977, 33, 433; V. Kh. Sabirov, M. A. Porai-Koshits and Yu. T. Struchkov, Koord. Khim., 1993, 19, 81; Ch. Vansent, H. O. Desseyn, V. Tangoulis, C. P. Raptopoulou, A. Terzis and S. P. Perlepes, Polyhedron, 1995, 15–16, 2115.
17. B. Kurzak, R. Matczak-Jon and M. Hoffmann, J. Coord. Chem., in the press.
18. N. Sampson and P. A. Bartlett, J. Org. Chem., 1987, 53, 4500; J. Rahil and R. F. Pratt, Biochemistry, 1993, 32, 10 763; B. P. Morgan, D. R. Holland, B. W. Mathews and P. A. Bartlett, J. Am. Chem. Soc., 1994, 116, 3251; A. Mucha, P. Kafarski, H.-J. Cristau and F. Plenat, Tetrahedron, 1994, 50, 12 743; R. Hirschman, K. H. Jager, C. M. Taylor, W. Moore, P. A. Sprengler, J. Witherington, B. W. Philips and A. B. Smith III, J. Am. Chem. Soc., 1995, 117, 6370; W. P. Malachowski and J. K. Coward, J. Org. Chem., 1996, 59, 7616, 7625.
19. W. Sawka-Dobrowolska, T. Głowiak and J. Kowalik, Acta Crystallogr., Sect. C, 1992, 48, 286 and refs. therein.
20. W. Sawka-Dobrowolska, T. Głowiak and Z. Siatecki, Acta Crystallogr., Sect. C, 1987, 43, 1942.
21. G. A. Jeffrey, J. R. Ruble, R. K. McMullen, D. J. DeFress, J. S. Binkley and J. A. Pople, Acta Crystallogr., Sect. B, 1980, 36, 2292.
22. A. Stein, Ch. W. Lehman and P. Luger, J. Am. Chem. Soc., 1992, 114, 7684; Y.-L. Lam, L.-L. Koch and H.-H. Huang, Acta Crystallogr., Sect. C, 1996, 52, 397; B. Sheldrick, D. Akrigg, M. I. Page and G. Cox, Acta Crystallogr., Sect. C, 1987, 47, 595.