On the mechanism of the oxygen transfer to sulfoxides by (peroxo)[tris(hydroxyalkyl)amine]TiIV complexes - Evidence for a metal-template-assisted process

European Journal of Organic Chemistry

Volumn , Issue 3, 2003, Pages 507-511

  Bonchio, Marcella ^a   Bortolini, Olga ^b   Licini, Giulia ^a   Moro, Stefano ^a   Nugent, William A ^c  

^a UNIVERSITY OF PADOVA   (Italy)

^b UNIVERSITY OF FERRARA   (Italy)

^c BRISTOL MYERS SQUIBB   (United States)

Author keywords

Homogeneous catalysis; N,O ligands; Oxidations; Sulfoxides; Titanium

Indexed keywords

LIGAND; METAL COMPLEX; OXYGEN; SULFOXIDE; TITANIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; MASS SPECTROMETRY; MICHAELIS MENTEN KINETICS; MOLECULAR INTERACTION; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0037322839     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200390087     Document Type: Article

References (48)

1. F. Di Furia, G. Licini, G. Modena, R. Motterle, W. A. Nugent, J. Org. Chem. 1996, 61, 5175-5177.
2. G. Licini, M. Bonchio, G. Modena, W. A. Nugent, Pure Appl. Chem. 1999, 71, 463-472.
3. For other stereoselective sulfoxidations involving cooperative asymmetric oxidation and kinetic resolution, see reference 21 in: M. Bonchio, G. Licini, F. Di Furia, S. Mantovani, G. Modena, W. A. Nugent, J. Org. Chem. 1999, 64, 1326-1330.
4. M. Bonchio, S. Calloni, F. Di Furia, G. Licini, G. Modena, S. Moro, W. A. Nugent, J. Am. Chem. Soc. 1997, 119, 6935-6936.
5. M. Selke, M. F. Sisemore, J. S. Valentine, J. Am. Chem. Soc. 1996, 118, 2008-2012.
6. M. Selke, J. S. Valentine, J. Am. Chem. Soc. 1998, 120, 2652-2653.
7. 0 complexes has also been proposed by other authors (see refs.).
8. W. A. Herrmann, R. V. Fischer, J. D. G. Correia, J. Mol. Catal. 1994, 94, 213-223.
9. M. M. Abu-Omar, J. H. Espenson, Organometallics 1996, 15, 3543-3549.
10. K. N. Brown, J. H. Espenson, Inorg. Chem. 1996, 35, 7211-7216.
11. W. Adam, M. N. Korb, K. J. Roschmann, C. R. Saha-Möller, J. Org. Chem. 1998, 63, 3423-3428.
12. W. Adam, C. M. Mitchell, C. R. Saha-Möller, T. Selvam, O. Weichold, J. Mol. Catal. A 2000, 154, 251-255.
13. Complex 2 has been demonstrated to attack preferentially at non-coordinated electron-rich sulfur centers as in sulfides, see ref.
14. N. S. Issacs, Physical Organic Chemistry, Longman Scientific Technical, Harlow, 1987, pp. 626-631.
15. M. Bonchio, G. Licini, G. Modena, S. Moro, O. Bortolini, P. Traldi, W. A. Nugent, Chem. Commun. 1997, 869-870.
16. M. Bonchio, G. Licini, G. Modena, O. Bortolini, S. Moro, W. A. Nugent, J. Am. Chem. Soc. 1999, 121, 6258-6268, and references cited therein.
17. 4SOMe has been reinvestigated at lower catalyst and hydroperoxide concentration (see Exp. Sect.) in order to slow down the process rate and allow an accurate kinetic analysis in the whole range of substrate concentrations examined.
18. -1
19. L. P. Hammett, J. Am. Chem. Soc. 1937, 59, 96-103.
20. H. H. Jaffe, Chem. Rev. 1953, 53, 191-261.
21. S. Rabe, U. Müller, Z. Naturforsch., Teil B 1997, 52, 1291-1295.
22. T.-Y. Hwang, J.-Y. Cho, M.-K. Jiang, H.-M. Gau, Inorg. Chim, Acta 2000, 303, 190-198.
23. 6]DMSO (up to 260 equiv.) showed a modest broadening of all resonances in the whole range of temperature explored (from -60 to +50 °C). This behaviour, which may be ascribed to the fast equilibria in solution, did not provide any structural evidence of DMSO coordination to complex 1.
24. ESI-MS experiments were performed under the same reported experimental conditions.
25. +}.
26. +, carrying both alkoxide and sulfoxide residues, could be detected by ESI-MS at m/z = 555.
27. IV protonated complexes, and it is indicative of the coordination of the tris-(hydroxyalkyl)amine to the metal center. In fact, upon CID, the free protonated tris(hydroxyalkyl)amines lose one, two or three water molecules.
28. + cation, was observed.
29. M. Calligaris, O. Carugo, Coord. Chem. Rev. 1996, 153, 83-154.
30. M. Calligaris, Croat. Chim. Acta 1999, 72, 147-169.
31. S. S. Xantheas, T. H. Dunning, J. Phys. Chem. 1993, 97, 6616-6627.
32. B. A. Smart, C. H. Schiesser, J. Comput. Chem. 1995, 15, 1055-1066.
33. P. J. A. Ruttink, P. C. Burgers, J. T. Francis, J. K. Terlouw, J. Phys. Chem. 1996, 100, 9694-9697.
34. F. Tureček, J. Phys. Chem. 1998, 102, 4703-4713.
35. A. P. Scott, L. Random, J. Phys. Chem. 1996, 100, 16502-16513.
36. M. Stener, J. Mol. Struct. (THEOCHEM) 2000, 497, 91-104.
37. D. R. Boyd, N. D. Sharma, S. A. Haughey, M. A. Kennedy, B. T. McMurray, G. N. Sheldrake, C. C. R. Allen, H. Dalton, K. Sproule, J. Chem. Soc., Perkin Trans. 1 1998, 1929-1934.
38. F. Fringuelli, R. Pellegrino, O. Piermatti, F. Pizzo, Synth. Commun. 1994, 24, 2665-2674.
39. R. Annunziata, M. Cinquini, F. Cozzi, L. Raimondi, G. Licini, Tetrahedron 1991, 47, 3869-3886.
40. L. Favretto, W.A. Nugent, G. Licini, Tetrahedron Lett. 2002, 43, 2581-2584 and references therein.
41. M. Frisch, G. W. Trucks, H. Schlegel, G. Scuseria, M. Robb, J. Cheeseman, V. Zakrzewski, J. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. Millam, A. Daniels, K. Kudin, M. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian98 (revision A.7), Gaussian, Inc, Pittsburgh, PA, 1998.
42. A. J. H. Wachters, J. Chem. Phys. 1970, 52, 1033-1036.
43. P. J. Hay, J. Chem. Phys. 1977, 66, 4377-4384.
44. M. J. Frisch, J. A. Pople, J. S. Binkley, J. Chem. Phys. 1984, 80, 3265-3269.
45. T. Clark, J. Chandrasekhar, G. W. Spitznagel, P. v. R. Schleyer, J. Comput. Chem. 1983, 4, 294-301.
46. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
47. P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283.
48. P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299-310.