Distinguishing Rate-Limiting Electron versus H-Atom Transfers in Cu 2(O2)-Mediated Oxidative N-Dealkylations: Application of Inter- versus Intramolecular Kinetic Isotope Effects

Journal of the American Chemical Society

Volumn 125, Issue 42, 2003, Pages 12670-12671

  Shearer, Jason ^a   Zhang, Christiana Xin ^a   Hatcher, Lanying Q ^a   Karlin, Kenneth D ^a  

^a JOHNS HOPKINS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER; CYTOCHROME P450; DICHLOROMETHANE; DOPAMINE BETA MONOOXYGENASE; IRON; ISOTOPE; METHYLAMINE; MONOPHENOL MONOOXYGENASE; N,N DIMETHYLANILINE; OXIDE; PORPHYRIN; TETRAHYDROFURAN;

ARTICLE; CHEMICAL BOND; COMPLEX FORMATION; DEALKYLATION; DISSOCIATION; ELECTRON TRANSPORT; ENTHALPY; HYDROXYLATION; OXIDATION; PROTON TRANSPORT; REDUCTION;

ALKYLATION; ANILINE COMPOUNDS; COPPER; ELECTRONS; HYDROGEN; KINETICS; OXIDATION-REDUCTION; OXYGEN;

EID: 0142072628     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0359409     Document Type: Article

References (27)

1. Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev. 1996, 96, 2563-2605.
2. (a) Que, L., Jr.; Tolman, W. B. Angew. Chem., Int. Ed. 2002, 41, 1114.
3. (b) Stack, T. D. P. Dalton Trans. 2003, 1881-1889.
4. Francisco, W. A.; Blackburn, N. J.; Klinman, J. P. Biochemistry 2003, 42, 1813-1819.
5. Pidcock, E.; Obias, H. V.; Zhang, C. X.; Karlin, K. D.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 7841-7847.
6. Itoh, S.; Taki, M.; Nakao, H.; Holland, P. L.; Tolman, W. B.; Que, L., Jr.; Fukuzumi, S. Angew. Chem., Int. Ed. 2000, 39, 398-400.
7. Mahapatra, S.; Halfen, J. A.; Tolman, W. B. J. Am. Chem. Soc. 1996, 118, 11575-11586.
8. Zhang, C. X.; Liang, H.-C.; Kim, E.-i.; Shearer, J.; Helton, M. E.; Kim, E.; Kaderli, S.; Incarvito, C. D.; Zuberbühler, A. D.; Rheingold, A. L.; Karlin, K. D. J. Am Chem. Soc. 2003, 125, 634.
9. Henson, M. J.; Vance, M. A.; Zhang, C. X.; Liang, H.-C.; Karlin, K. D.; Solomon, E. I. J. Am Chem. Soc. 2003, 125, 5186-5192.
10. 2N vs R′ = H).7
11. (a) Karki, S. B.; Dinnocenzo, J. P.; Jones, J. P.; Korzekwa, K. R. J. Am. Chem. Soc. 1995, 117, 3657-3664.
12. (b) Goto, Y.; Watanabe, Y.; Fukuzumi, S.; Jones, J. P.; Dinnocenzo, J. P. J. Am. Chem. Soc. 1998, 120, 10762-10763.
13. (c) Dinnocenzo, J. P.; Karki, S. B.; Jones, J. P. J. Am. Chem. Soc. 1993, 115, 7111-7116.
14. (d) Manchester, J. I.; Dinnocenzo, J. P.; Higgins, L. A.; Jones, J. P. J. Am. Chem. Soc. 1997, 119, 5069-5070.
15. (e) Baciocchi, E.; Lanzalunga, O.; Lapi, A.; Manduchi, L. J. Am. Chem. Soc. 1998, 120, 5783-5787.
16. (f) Okazaki, O.; Guengerich, F. P. J. Biol. Chem. 1993, 268, 1546-1552.
17. (g) Guengerich, F. P.; Yun, C.-H.; Macdonald, T. L. J. Biol. Chem. 1996, 271, 27321-27329.
18. (a) Sato, H.; Guengerich, F. P. J. Am. Chem. Soc. 2000, 122, 8099-8100.
19. (b) Stearns, R. A.; de Monetellano, P. R. O. J. Am. Chem. Soc. 1985, 107, 4081-4082.
20. (c) Hall, L. R.; Hanzlik, R. P. J. Biol. Chem. 1990, 265, 12349-12355.
21. Me2N, ∼90%.
22. See Supporting Information.
23. 2) core, and that the low isotope incorporation is due to exchange of the carbonyl oxygen with residual water in the solvent.13
24. Johnson, C. D. The Hammett Equation; Cambridge University Press; Cambridge, U.K., 1973.
25. Going from a 10- to 100-fold excess of substrate did not change the relative yields.
26. D could reach a maximum of 23.1).
27. Me2N will not.