Multiplicity of reaction pathways in the processes of oxygen transfer to secondary amines by Mo(VI) and W(VI) peroxo complexes

Journal of Organic Chemistry

Volumn 61, Issue 18, 1996, Pages 6381-6387

  Ballistreri, Francesco P ^a   Barbuzzi, Elena G M ^a   Tomaselli, Gaetano A ^b   Toscano, Rosa M ^a  

^a UNIVERSITY OF CATANIA   (Italy)

^b UNIVERSITY OF PALERMO   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001704835     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960544c     Document Type: Article

References (22)

1. (a) Poulsen, L. L.; Kadlubar, F. F.; Ziegler, D. M. Arch. Biochem. Biophys. 1974, 164, 774-775.
2. (b) Sheldon, B.; Bruice, T. C. J. Am. Chem. Soc. 1980, 102, 6498-6503.
3. (a) Murahashi, S. I.; Mitsui, H.; Shiota, T.; Tsuda, T.; Watanabe, S. J. Org. Chem. 1990, 55, 1736-1744.
4. (b) Ballistreri, F. P.; Chiacchio, U.; Rescifina, A.; Tomaselli, G. A.; Toscano, R. M. Tetrahedron 1992, 48, 8677-8684.
5. (c) Tollari, S.; Bruni, S.; Bianchi, C. L.; Rainoni, M.; Porta, F. J. Mol. Catal. 1993, 83, 311-322.
6. (a) Arcoria, A.; Ballistreri, F. P.; Spina, E.; Tomaselli, G. A.; Toscano, R. M. Gazz. Chim. Ital. 1990, 120, 309-313.
7. (b) Ballistreri, F. P.; Tomaselli, G. A.; Toscano, R. M. J. Mol. Catal. 1991, 68, 269-275.
8. (c) Ballistreri, F. P.; Bazzo, A.; Tomaselli, G. A.; Toscano, R. M. J. Org. Chem. 1992, 57, 7074-7077.
9. Bartlett, P. D. Record. Chem. Progr. 1950, 11, 47-56. See also: Curci, R.; Edwards, J. O. In Organic Peroxides; Swern, D., Ed.; Wiley Interscience: New York, 1970; Vol. 1, pp 199-264 and references therein.
10. Bartlett, P. D. Record. Chem. Progr. 1950, 11, 47-56. See also: Curci, R.; Edwards, J. O. In Organic Peroxides; Swern, D., Ed.; Wiley Interscience: New York, 1970; Vol. 1, pp 199-264 and references therein.
11. Campestrini, S.; Di Furia, F. Tetrahedron 1994, 50, 5119-5131.
12. Di Furia, F.; Modena, G. Pure Appl. Chem. 1982, 54, 1853-1866.
13. Bortolini, O; Campestrini, S.; Di Furia, F.; Modena, G. J. Org. Chem. 1987, 52, 5467-5469.
14. Campestrini, S.; Di Furia, F.; Rossi, P.; Torboli, A. J. Mol. Catal. 1993, 83, 95-105.
15. Campestrini, S.; Conte, V.; Di Furia, F.; Modena, G. J. Org. Chem. 1988, 53, 5721-5724.
16. 3. Both substrates yield the same nitrone quantitatively, and the oxidation rate of N,N-dibenzylhydroxylamine is nearly 10 times larger than that of N,N-dibenzylamine. Thus, these findings seem to give support to the probable involvement of hydroxylamine as an intermediate in these oxidation processes.
17. Arcoria, A.; Ballistreri, F. P.; Tomaselli, G. A.; Di Furia, F.; Modena, G. J. Mol. Cat. 1984, 24, 189-196.
18. Cyclic voltammetry measurements, performed by Di Furia et al. (Bonchio, M.; Conte, V.; Di Furia, F.; Modena, G.; Moro, S.; Carofiglio, T.; Magno, F.; Pastore, P. Inorg. Chem. 1993, 32, 5797-5799), indicated for W peroxo complexes reduction peak potentials less negative than those observed for the corresponding Mo derivatives. Furthermore, the authors reported a good correlation between these reduction peak potentials and IR O-O bond frequencies. On the basis of these observations, it might be conceivable to assume that the LUMO of W peroxo complexes, involving the peroxide oxygens, is lower in energy than that of Mo peroxo complexes and, therefore, that W peroxo complexes have a Lewis acidity higher than that of Mo oxidants.
19. Webb, J. L. In Enzymes and Metabolic Inhibitors; Academic Press: New York, 1963; pp 52-68.
20. Mimoun, H.; Seree De Roche, I.; Sajus, L. Bull. Soc. Chim. Fr. 1969, 1481-1492.
21. Bortolini, O.; Campestrini, S; Di Furia, F.; Modena, G. J. Org. Chem. 1987, 52, 5093-5095.
22. Campestrini, S. Ph.D. Thesis, Padova University, 1988.