The complete and irreversible conversion of a cis carbon-substituted thiiranium ion into the trans isomer

Abstract

t-2-tert-Butyl-t-3-phenyl-r-1-methylthiiranium 1 isomerizes into the more stable (32.3 kJ mol^–1) t-2-tert-butyl-c-3-phenyl-r-1-methylthiiranium 2 in a complete and irreversible process (monitored by proton NMR at –30 °C) via an open benzylic carbenium ion.

References

1. G. Capozzi, G. Modena and L. Pasquato, The Chemistry of Sulphenyl Halides and Sulphenamides, ed. S. Patai, Wiley, Chichester, 1990, p. 403.
2. V. Lucchini, G. Modena and L. Pasquato, Gazz. Chim. Ital., 1997, 127, 177.
3. D. J. Pettit and G. K. Helmkamp, J. Org. Chem., 1963, 28, 2932.
4. G. I. Borodkin, Y. V. Gatilov, E. I. Chernyak and V. G. Shubin, Izv. Akad. Nauk SSSR, Ser. Kim., 1985, 2826 (Chem. Abstr., 1986, 105, 208686); G. I. Borodkin, Y. V. Gatilov, E. I. Chernyak and V. G. Shubin, Izv. Akad. Nauk SSSR, Ser. Kim., 1987, 2230 (Chem. Abstr., 1987, 108, 186453).
5. X. Huang, R. J. Batchelor, F. W. Einstein and A. J. Bennet, J. Org. Chem., 1994, 59, 7108.
6. L. Pasquato, R. Destro, V. Lucchini and G. Modena, Phosphorus Sulfur Silicon Relat. Elem., in the press.
7. G. Capozzi, O. De Lucchi, V. Lucchini and G. Modena, Tetrahedron Lett., 1975, 2603.
8. V. Lucchini, G. Modena and L. Pasquato, J. Am. Chem. Soc., 1988, 110, 6900; V. Lucchini, G. Modena and L. Pasquato, J. Am. Chem. Soc., 1991, 113, 6600.
9. Y. Kikuzono, T. Yamabe, S. Nagata, H. Kato and K. Fukui, Tetrahedron, 1974, 30, 2197; J. W. Gordon, G. H. Schmid and I. G. Csizmadia, J. Chem. Soc., Perkin Trans. 2, 1975, 1722.
10. G. H. Schmid and V. M. Csizmadia, Can. J. Chem., 1966, 44, 1338.
11. W. A. Smit, M. Z. Krimer and E. A. Vorobieva, Tetrahedron Lett., 1975, 2451; E. A. Vorobieva, M. Z. Krimer and W. A. Smit, Izv. Akad. Nauk SSSR, Ser. Kim., 1976, 2743.
12. For example: K. C. Nicolaou, T. Ladduwahetty, J. L. Randall and A. Chucholowski, J. Am. Chem. Soc., 1986, 108, 2466; T. Sato, J. Otera and H. Nozaki, J. Org. Chem., 1990, 55, 6116; K. Kudo, Y. Hashimoto, M. Sukegawa, M. Hasegawa and K. Saigo, J. Org. Chem., 1993, 58, 579; D. K. Jones and D. C. Liotta, Tetrahedron Lett., 1993, 34, 7209; D. K. Jones and D. C. Liotta, Adv. Mol. Model., 1995, 3, 67.
13. V. Lucchini, G. Modena, M. Pasi and L. Pasquato, J. Org. Chem., 1997, 62, 7018.
14. M. Fachini, V. Lucchini, G. Modena, M. Pasi and L. Pasquato, J. Am. Chem. Soc., 1999, 121, 3944.
15. V. Lucchini, G. Modena and L. Pasquato, J. Chem. Soc., Chem. Commun., 1994, 1565.
16. Z.-Y. Yang and D. J. Burton, Tetrahedron Lett., 1990, 31, 1369.
17. H. C. Brown and S. K. Gupta, J. Am. Chem. Soc., 1972, 94, 4370.