Applicability and mathematical verification of the reactivity–selectivity principle in the oxidation of thioanisoles by oxo(salen)manganese(V) complexes 

Abstract

The second-order rate constants for the oxidation of various para-substituted thioanisoles with substituted oxo(salen)manganese(V) complexes have been measured spectrophotometrically in acetonitrile at 25 °C. Electron-withdrawing substituents in thioanisoles and electron-releasing substituents in oxo(salen)Mn^V complexes decrease the rate of oxidation. Correlation analyses show the presence of an inverse relationship between reactivity and selectivity in the reactions of various thioanisoles with a given oxo(salen)Mn^V complex and also in various oxo(salen)Mn^V complexes with a given thioanisole. Mathematical treatment of the results has also been carried out.

References

1. C. D. Johnson, Chem. Rev., 1975, 75, 755.
2. A. Pross, Adv. Phys. Org. Chem., 1977, 14, 69.
3. C. D. Johnson, Tetrahedron, 1980, 36, 3461 and references cited therein.
4. O. Exner, J. Chem. Soc., Perkin Trans. 2, 1993, 973.
5. (a) C. Srinivasan, P. Kuthalingam and N. Arumugam, J. Chem. Soc., Perkin Trans. 2, 1980, 170; (b) D. Bethell, A. E. Graham, J. P. Heer, O. Markopoulou, P. C. B. Page and B. K. Park, J. Chem. Soc., Perkin Trans. 2, 1993, 2161; (c) I. Lee, H. J. Koh, Y. S. Park and H. W. Lee, J. Chem. Soc., Perkin Trans. 2, 1993, 1575.
6. E. Buncel and C. J. Chanqui, J. Org. Chem., 1980, 45, 2825.
7. R. H. Holm, Chem. Rev., 1987, 87, 1401.
8. B. Meunier, Chem. Rev., 1992, 92, 1411.
9. R. S. Drago, Coord. Chem. Rev., 1992, 117, 185.
10. (a) R. Sato and Y. Omuru, Cytochrome P-450, Kodansa, Tokyo and Academic Press, New York, 1980; (b) H. L. Holland, Chem. Rev., 1988, 88, 473; (c) A. G. Cochran and P. G. Schultz, J. Am. Chem. Soc., 1990, 112, 9414; (d) M. H. Gelb, W. A. Toscano, Jr. and S. C. Sligar, Proc. Natl. Acad. Sci., 1982, 79, 5758; (e) J. Amesz, Biochim. Biophys. Acta, 1983, 1, 726.
11. (a) E. Guilmet and B. Meunier, Tetrahedron Lett., 1982, 23, 2449; (b) 1980, 21, 4449; (c) J. T. Groves and M. K. Stern, J. Am. Chem. Soc., 1988, 110, 8628; (d) P. L. Anelli, S. Banfi, F. Montanari and S. Quici, J. Chem. Soc., Chem. Commun., 1989, 779.
12. W. Zhang and E. N. Jacobsen, J. Org. Chem., 1991, 56, 2296.
13. P. Pietikainen, Tetrahedron Lett., 1995, 36, 319.
14. P. Pietikainen, Tetrahedron Lett., 1994, 35, 941.
15. E. G. Samsel, K. Srinivasan and J. K. Kochi, J. Am. Chem. Soc., 1985, 107, 7606.
16. K. Srinivasan, P. Michuad and J. K. Kochi, J. Am. Chem. Soc., 1986, 108, 2309.
17. B. Rihter, S. SriHari, S. Hunter and J. Masnovi, J. Am. Chem. Soc., 1993, 115, 3918.
18. A. Chellamani, N. M. I. Alhaji, S. Rajagopal, R. Sevvel and C. Srinivasan, Tetrahedron, 1995, 51, 12677.
19. R. Sevvel, S. Rajagopal, C. Srinivasan, N. M. I. Alhaji and A. Chellamani, submitted for publication.
20. M. Palucki, P. Hanson and E. N. Jacobsen, Tetrahedron Lett., 1992, 33, 7111.
21. C. Srinivasan, S. Rajagopal and A. Chellamani, J. Chem. Soc., Perkin Trans. 2, 1990, 1839.
22. E. Baciocchi, D. Intini, A. Piermattei, C. Roe and B. Ruzziconi, Gazz. Chim. Ital., 1989, 119, 646.
23. R. Curci, S. Giannattasio, O. Sciacovelli and L. Troisi, Tetrahedron, 1984, 40, 2763.
24. F. Ruff and A. Kucsman, J. Chem. Soc., Perkin Trans. 2, 1985, 683.
25. H. G. Hanthal, H. Onderka and W. Pritzkow, J. Prakt. Chem., 1969, 82, 311.
26. (a) S. Oae, Y. Watanabe and K. Fujimori, Tetrahedron Lett., 1982, 1189; (b) Y. Watanabe, T. Numata, T. Iyanagi and S. Oae, Bull. Chem. Soc. Jpn., 1981, 54, 1163.
27. J. H. Acquaye, J. G. Muller and K. J. Takeuchi, Inorg. Chem., 1993, 32, 160.
28. A. E. Miller, J. J. Bischoff, C. Bizub, P. Luminoso and S. Smiley, J. Am. Chem. Soc., 1986, 108, 7773.
29. C. Srinivasan, A. Chellamani and S. Rajagopal, J. Org. Chem., 1985, 50, 1201.
30. R. V. Sendega, R. V. Vizgert and M. K. Mikhalevich, Reakts. Sposobnost Org. Soedin. (Tartu), 1970, 7, 512.
31. H. Zahn and H. Zuber, Chem. Ber., 1953, 86, 180.
32. V. Baliah and M. Uma, Tetrahedron, 1963, 19, 455.
33. H. Saltzman and J. G. Sharefkin, Organic Syntheses, Vol. V, New York, Wiley, 1973, 658.
34. T. Takata, R. Tajima and W. Ando, Phosphorous and Sulfur, 1983, 16, 67.
35. W. Ando, R. Tajima and T. Takata, Tetrahedron Lett., 1982, 23, 1685.