Theoretical calculations of carbon-oxygen bond dissociation enthalpies of peroxyl radicals formed in the autoxidation of lipids

Journal of the American Chemical Society

Volumn 125, Issue 19, 2003, Pages 5801-5810

  Pratt, Derek A ^a   Mills, Jeremy H ^a   Porter, Ned A ^a  

^a VANDERBILT UNIVERSITY SCHOOL OF MEDICINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON-OXYGEN BONDS;

CARBON; CHEMICAL BONDS; DISSOCIATION; ENTHALPY; LIPIDS; OXIDATION; OXYGEN;

FREE RADICALS;

BENZYLIC RADICAL; CARBON; LIPID; OXYGEN; PEROXY RADICAL; RADICAL; UNCLASSIFIED DRUG; UNSATURATED FATTY ACID;

ACCELERATION; ARTICLE; CALCULATION; CHEMICAL BOND; CONJUGATION; CORRELATION ANALYSIS; DENSITY; DIFFUSION; DISSOCIATION; ELECTRON; ENTHALPY; EXPERIMENT; HYDROGEN BOND; LIPID PEROXIDATION; OXIDATION; THEORY;

ALPHA-LINOLENIC ACID; ARACHIDONIC ACID; CARBON; HYDROGEN BONDING; LIPIDS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR CONFORMATION; OXIDATION-REDUCTION; OXYGEN; PEROXIDES; THERMODYNAMICS;

EID: 0037620493     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034182j     Document Type: Article

References (51)

1. (a) Marnett, L. J. Carcinogenesis 2000, 21, 361-370.
2. (b) Sevanian, A.; Ursini, F., Free Radical Biol. Med. 2000, 29, 306-311.
3. (c) Spiteller, G.; Spiteller, D.; Jira, W.; Kiessling, U.; Dudda, A.; Weisser, M.; Hecht, S.; Schwarz, C. Peroxide Chem. 2000, 179-208.
4. (a) Steinburg, D.; Parhsarathy, S.; Carew, T. E.; Khoo, J. C.; Witztum, J. L. N. Engl. J. Med. 1989, 320, 915-924.
5. (b) Chisholm, G. M.: Steinburg, D. Free Radical Biol. Med. 2000, 28, 1815-1826.
6. Chan, H. W.-S.; Levett, G. Lipids 1977, 12, 99-104.
7. (a) Porter, N. A. Acc. Chem. Res. 1986, 19, 262-268.
8. (b) Porter, N. A.: Caldwell, S. E.; Mills, K. A. Lipids 1995, 30, 277-290.
9. Porter, N. A.; Wujek, D. G. J. Am. Chem. Soc. 1984, 106, 2626-2629.
10. (a) Brash, A. R. Lipids 2000, 35, 947-952.
11. (b) Tallman, K. A.; Pratt, D. A.; Porter, N. A. J. Am. Chem. Soc. 2001, 123, 11827-11828.
12. Luo, Y.-R. Handbook of Bond Dissociation Energies in Organic Compounds; CRC Press: Boca Raton, FL, 2003; pp 166-170. Virtually all ROO-H BDEs are roughly 88 kcal/mol.
13. DiLabio, G. A.; Pratt, D. A.; LoFaro, A. D.; Wright, J. S. J. Phys. Chem. A 1999, 103, 1653-1661.
14. Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1998, 109, 7764.
15. Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1999, 110, 4703-4709.
16. Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744-2765.
17. Trenwith, A. B. J. Chem. Soc., Faraday Trans. 1 1982, 78, 3131-3136. This C-H BDE, also measured by Clark et al. reference (Clark, K. B.: Culshaw, P. N.: Griller, D.; Lossing, F. P.; Martinho Simoes, J. A.: Walton, J. J. Org. Chem. 1991, 56. 5535-5539.) by photoacoustic calorimetry, was found to be 77 kcal/mol. However, upon revision of this value to 82 kcal/ mol to correct for solvation (Laarhoven, L. J. J.: Mulder, P.; Wayner, D. D. M. Acc. Chem. Res. 1999, 32, 342-349), the authors admit that addition of t-BuO to the double bond takes place under the experimental conditions, and the two processes cannot be deconvoluted, leading to an artificially high C-H BDE. Hence, we consider the older gas phase thermolysis value obtained by Trenwith to be most reliable.
18. Trenwith, A. B. J. Chem. Soc., Faraday Trans. 1 1982, 78, 3131-3136. This C-H BDE, also measured by Clark et al. reference (Clark, K. B.: Culshaw, P. N.: Griller, D.; Lossing, F. P.; Martinho Simoes, J. A.: Walton, J. J. Org. Chem. 1991, 56. 5535-5539.) by photoacoustic calorimetry, was found to be 77 kcal/mol. However, upon revision of this value to 82 kcal/ mol to correct for solvation (Laarhoven, L. J. J.: Mulder, P.; Wayner, D. D. M. Acc. Chem. Res. 1999, 32, 342-349), the authors admit that addition of t-BuO to the double bond takes place under the experimental conditions, and the two processes cannot be deconvoluted, leading to an artificially high C-H BDE. Hence, we consider the older gas phase thermolysis value obtained by Trenwith to be most reliable.
19. Trenwith, A. B. J. Chem. Soc., Faraday Trans. 1 1982, 78, 3131-3136. This C-H BDE, also measured by Clark et al. reference (Clark, K. B.: Culshaw, P. N.: Griller, D.; Lossing, F. P.; Martinho Simoes, J. A.: Walton, J. J. Org. Chem. 1991, 56. 5535-5539.) by photoacoustic calorimetry, was found to be 77 kcal/mol. However, upon revision of this value to 82 kcal/ mol to correct for solvation (Laarhoven, L. J. J.: Mulder, P.; Wayner, D. D. M. Acc. Chem. Res. 1999, 32, 342-349), the authors admit that addition of t-BuO to the double bond takes place under the experimental conditions, and the two processes cannot be deconvoluted, leading to an artificially high C-H BDE. Hence, we consider the older gas phase thermolysis value obtained by Trenwith to be most reliable.
20. Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds, 2nd ed. Chapman and Hall: London, 1986.
21. Pratt, D. A.; de Heer, M. I.; Mulder, P.; Ingold, K. U. J. Am. Chem. Soc. 2001, 123, 5518-5526.
22. Pratt, D. A.; DiLabio, G. A.; Brigati, G.; Pedulli, G. F.; Valgimigli, L. J. Am. Chem. Soc. 2001, 123, 4625-4626.
23. Pratt, D. A.; DiLabio, G. A.; Valgimigli, L.; Pedulli, G. F.; Ingold, K. U. J. Am. Chem. Soc. 2002, 124, 11085-11092.
24. Wright, J. S.; Johnson, E. R.; DiLabio, G. A. J. Am. Chem. Soc. 2001, 123, 1173-1183.
25. Montgomery, J. A., Jr.; Ochterski, J. W.; Petersson, G. A. J. Chem. Phys. 1994. 101, 5900. Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A., Jr. J. Chem. Phys. 1996, 104, 2598.
26. Montgomery, J. A., Jr.; Ochterski, J. W.; Petersson, G. A. J. Chem. Phys. 1994. 101, 5900. Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A., Jr. J. Chem. Phys. 1996, 104, 2598.
27. It should be pointed out that the B3LYP-HLM C-H BDE for 13-pentadiene is in good agreement with the experimental. G3, and G3MP2 values despite the fact that the pentadienyl radical formed upon C-H homolysis is the same as that for 1,4-pentadiene, This suggests that the observation that DFT underestimates X-H BDEs (X = O, N) for compounds with increasingly weak bonds is not because of a problem with how the open shell radical is handled but instead the closed-shell precursor.
28. Hrovat, D. A.; Borden, W. T. J. Phys. Chem. 1994, 98, 10460-10464.
29. The rate constant of β-fragmentation of the nonconjugated allylbenzylperoxyl radical to the allylbenzyl radical is 1 order of magnitude slower than the rate constant of β-fragmentation of the nonconjugated pentadienylperoxyl of methyl linoleate. Given the plots in Figures 5 and 6, we translate this to a difference in RSE of roughly 2 kcal/mol.
30. Spin densities derived from unrestricted wave functions are reported. Although spin densities from restricted wave functions yielded spin distributions that follow the same trend as those from the unrestricted calculations, they do not reproduce experimental relative spin distributions as well. For example, the spin distribution in the benzyl radical from a ROB3LYP/6-311+G(2d, 2p) calculation places spin at the benzylic, ortho, and para positions in a ratio of 5.31:1:1.27.
31. Dust, J. M.; Arnold, D. R. J. Am. Chem. Soc. 1983, 105, 1221-1227.
32. Davies, A. G.; Griller, D.; Ingold, K. U.; Lindsay, D. A.; Walton, J. C. J. Chem. Soc., Perkin Trans. 2 1981, 633.
33. DiLabio, G. A.; Pratt, D. A. J. Phys. Chem. A 2000, 104, 1938-1943.
34. Boyd, S. L.; Boyd, R. J.; Shi, Z.; Barclay, L. R. C.; Porter, N. A. J. Am. Chem. Soc. 1993, 115, 687-693.
35. Kranenburg, M.; Ciriano, M. V.; Cherkasov, A.; Mulder, P. J. Phys. Chem. A 2000, 104, 915-921.
36. Knyazev, V. D.; Slagle, I. R. J. Phys. Chem. A 1998, 102, 1770-1778.
37. Fenter, F. F.; Noziere, B.; Caralp, P.; Lesclaux. R. Int. J. Chem. Kinet. 1994, 26, 171.
38. Knyazev, V. D.; Slagle, I. R. J. Phys. Chem. A 1998, 102, 8932-8940.
39. Zils, R.; Inomata, S.; Imamura, T.; Miyoshi, A.; Washida, N. J. Phys. Chem. A 2001, 105, 1277-1282.
40. Pratt, D. A.; Porter, N. A. Org. Lett. 2003, 5, 387-390.
41. Porter, N. A.; Mills, K. A.; Carter, R. L. J. Am. Chem. Soc. 1994, 116, 6690-6696.
42. Bascetta, E.; Gunstone, F. D.; Walton, J. C. J. Chem. Soc., Perkin Trans. 2 1983, 603-613.
43. Howard, J. A. Adv. Free Radical Chem. 1972, 4, 49-173.
44. It is worth noting that the propagating radical in autoxidations of cyclohexadienes, 9,10-dihydroanthracene, and 1,4-dihydronaphthalene was likely hydroperoxyl and that rate constants for cyclopentane and cyclohexane are for reactions with t-BuOO. All rate constants are reported as measured and not on a per hydrogen basis.
45. Howard, J. A.; Bennett, J. E.; Brunton, G. Can. J. Chem. 1981, 59, 2253-2260.
46. Howard, J. A.; Chenier, J. H. B.; Yamada, T. Can. J. Chem. 1982, 60, 2566-2572.
47. β = -0.46-(C-OOBDE) + 9.9.
48. Burton, G. W.; Ingold, K. U. Science 1984, 224, 569. It has been suggested that β-carotene reacts with peroxyl radicals by addition to form a delocalized carbon-centered radical, which does not add oxygen and carry the chain. Although it is well-documented that addition occurs to give an intermediate carotenoid carbon radical, the fate of this radical remains unclear.
49. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgonery, J. A., Jr.: Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A7; Gaussian, Inc., Pittsburgh, PA, 1998.
50. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502.
51. Nelsen S. F. Bartlett, P. D. J. Am. Chem. Soc. 1966, 88, 137-143.