Thermodynamics and kinetics of the hydride-transfer cycles for 1-aryl-1,4-dihydronicotinamide and its 1,2-dihydroisomer

Chemistry - A European Journal

Volumn 9, Issue 16, 2003, Pages 3937-3945

  Zhu, Xiao Qing ^a   Cao, Lei ^a   Liu, Yang ^a   Yang, Yuan ^a   Lu, Jin Yong ^a   Wang, Jian Shuang ^a   Cheng, Jin Pei ^a  

^a NANKAI UNIVERSITY   (China)

Author keywords

Hydride transfer; Kinetics; Nicotinamide; Thermodynamics

Indexed keywords

ACTIVATION ENERGY; REACTION KINETICS; SYNTHESIS (CHEMICAL); THERMODYNAMICS;

KINETIC ANALYSIS;

ISOMERS;

1,2 DIHYDRONICOTINAMIDE DERIVATIVE; 1,2 DIHYDROPYRIDINE DERIVATIVE; 1,4 DIHYDRONICOTINAMIDE DERIVATIVE; 1,4 DIHYDROPYRIDINE DERIVATIVE; DIHYDROPYRIDINE DERIVATIVE; NICOTINAMIDE; PYRIDINIUM DERIVATIVE; REDUCED NICOTINAMIDE ADENINE DINUCLEOTIDE PHOSPHATE; UNCLASSIFIED DRUG;

ABSORPTION SPECTROSCOPY; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTROCHEMISTRY; ENERGY; ENTHALPY; ENTROPY; ISOMER; KINETICS; OXIDATION; SYNTHESIS; THERMODYNAMICS; ULTRAVIOLET SPECTROSCOPY;

ELECTRON TRANSPORT; HYDROGEN; KINETICS; MODELS, CHEMICAL; MOLECULAR STRUCTURE; NAD; NADP; NIACINAMIDE; OXIDATION-REDUCTION; PROTONS; PYRIDINES; SPECTROPHOTOMETRY, ULTRAVIOLET; STEREOISOMERISM; STRUCTURE-ACTIVITY RELATIONSHIP; THERMODYNAMICS;

EID: 0042365046     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200304714     Document Type: Article

References (68)

1. J. Rydstrom, J. Hoeck, L. Ernster, Nicotinamide Nucleotide Transhydrogenases in "The Enzymes, Vol. XIII" (Ed.: P. D. Boyer), Academic Press, New York, 1976.
2. F. H. Westhermer, Ad. Enzymol. 1962, 24, 469.
3. S. Chaykin, Annu. Rev. Biochem. 1967, 36, 149.
4. a) U. Eisner, J. Kuthan, Chem. Rev. 1972, 72, 1 and references therein;
5. b) Pyridine and its Derivatives, Part 1 (Ed.: E. Klingsberg), Wiley, New York, 1960.
6. a) S. Fukuzumi, S. Koumitsu, K. Hironaka, T. Tanaka, J. Am. Chem. Soc. 1987, 109, 305;
7. b) M. F. Powell, J. C. Wu, T. C. Bruice, J. Am. Chem. Soc. 1984, 106, 3850;
8. c) O. Almarsson, T. C. Bruice, J. Am. Chem. Soc. 1993, 115, 2125;
9. d) A. Ohno, H. Yamamoto, S. Oka, J. Am. Chem. Soc. 1981, 103, 2041;
10. e) L. L. Miller, J. R. Valentine, J. Am. Chem. Soc. 1988, 110, 3982;
11. f) H. C. Lo, O. Buriez, J. B. Kerr, R. H. Fish, Angew. Chem. 1999, 111, 1524; Angew. Chem. Int. Ed. 1999, 38, 1429;
12. f) H. C. Lo, O. Buriez, J. B. Kerr, R. H. Fish, Angew. Chem. 1999, 111, 1524; Angew. Chem. Int. Ed. 1999, 38, 1429;
13. g) B. W. Carlson, L. L. Miller, J. Am. Chem. Soc. 1983, 105, 7454;
14. h) N. Kanomata, M. Suzuki, M. Yoshida, T. Nakata, Angew. Chem. 1998, 110, 1506; Angew. Chem. Int. Ed. 1998, 37, 1410;
15. h) N. Kanomata, M. Suzuki, M. Yoshida, T. Nakata, Angew. Chem. 1998, 110, 1506; Angew. Chem. Int. Ed. 1998, 37, 1410;
16. i) X.-Q. Zhu, Y. Liu, B. J. Zhao, J.-P. Cheng, J. Org. Chem. 2001, 66, 370;
17. j) J.-P. Cheng, Y. Lu, X.-Q. Zhu, L. Mu, J. Org. Chem. 1998, 63, 6108;
18. k) X.-Q. Zhu, Y. Liu, B.-J. Zhao, J.-P. Cheng, J. Org. Chem. 2001, 66, 370.
19. a) A. I. Kruppa, M. B. Taraban, N. E. Polyakov, T. V. Leshina, J. Photochem. Photobiol. A Chem. 1993, 73, 159;
20. b) X.-Q. Zhu, B.-J. Zhao, J.-P. Cheng, J. Org. Chem. 2000, 65, 8158;
21. c) X.-Q. Zhu, Y.-C. Liu, J.-P. Cheng, J. Org. Chem. 1999, 64, 8980;
22. d) X.-Q. Zhu, H.-L. Zou, P.-W. Yuan, L. Cao, J.-P. Cheng, J. Chem. Soc. Perkin Trans. 2 2000, 1857;
23. e) B.-J. Zhao, X.-Q. Zhu, J.-Q. He, Z.-Z. Xia, J.-P. Cheng, Tetrahedron Lett. 2000, 41, 257.
24. a) Ö. Almarsso, A. Sinha, E. Gopinath, T. Bruice, J. Am. Chem. Soc. 1993, 115, 7093;
25. b) C. A. Coleman, J. G. Rose, C. J. Murray, J. Am. Chem. Soc. 1992, 114, 9755;
26. c) S. Fukuzumi, S. Mochizuki, T. Tanaka, Inorg. Chem. 1990, 29, 653;
27. d) P. Hapiot, J. Moiroux, J.-M. Saveant, J. Am. Chem. Soc. 1990, 112, 1337.
28. a) M. F. Powell, T. C. Bruice, J. Am. Chem. Soc. 1982, 104, 5834;
29. b) J. W. Bunting, S. Sindhuatmadja, J. Org. Chem. 1980, 45, 5411;
30. c) A. Anne, S. Fraoua, J. Moiroux, J.-M. Saveant, J. Am. Chem. Soc. 1996, 118, 3938;
31. d) A. Marcinek, J. Adamus, J. Gebicki, J. Phys. Chem. A 2000, 104, 724.
32. M. E. Brewster, J. J. Kaminski, Z. Gabanyi, K. Czako, A. Simay, N. Bodor, Tetrahedron 1989, 45, 4395.
33. a) R. M. Acheson, G. Paglietti, J. Chem. Soc. Perkin 1 1976, 45;
34. b) G. Paglietti, P. Sanna, A. Nuvole, J. Chem. Res. (S) 1983, 245; G. Paglietti, P. Sanna, A. Nuvole, J. Chem. Res. (M) 1983, 2326.
35. b) G. Paglietti, P. Sanna, A. Nuvole, J. Chem. Res. (S) 1983, 245; G. Paglietti, P. Sanna, A. Nuvole, J. Chem. Res. (M) 1983, 2326.
36. N. Kornblum, Angew. Chem. 1975, 87, 797; Angew. Chem. Int. Ed. Engl. 1975, 14, 734.
37. N. Kornblum, Angew. Chem. 1975, 87, 797; Angew. Chem. Int. Ed. Engl. 1975, 14, 734.
38. a) S. R. Logan, Fundamentals of Chemical Kinetics, Addison Wesley Longman, London, 1996, Chapter 2, p. 35;
39. b) Techniques of Chemistry, Volume VI Investigations of rates and mechanisms of reactions (Ed.: G. G. Hammes), 3rd ed., Parts I and II, New York, Wiley.
40. K. L. Handoo, J.-P. Cheng, V. D. Parker, J. Am. Chem. Soc. 1993, 115, 5067.
41. +/0), if the hydride transfer from the 1,4- or 1,2-dihydropyridnes to p-trifluoromethyl-benzylidenemalononitrile were initiated by single electron transfer, remarkable inhibitory effect on the two reaction rates would had been observed, when p-dinitrobenzene was added into the reaction mixtures.
42. -1 for the reactions with the 1,2-dihydropyridines see Table 5). Thus it is impossible that the hydride transfer from the dihydropyridines to S was initiated by single electron transfer.
43. N. S. Isaacs, Physical Organic Chemistry, 1st ed., Wiley, New York, 1987, Chapter 4.
44. J. W. Bunting, S. Sindhatmadja, J. Org. Chem. 1981, 46, 4211.
45. The values of ΔH‡ and ΔS‡ for the hydride transfer can be obtained from Table 3, since the initial hydride transfer is in rate-limiting process, the kinetic parameters for the reaction of S with the dihydropyridines may be due to the initial hydride transfer.
46. M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 2, p. 42.
47. Here we made an assumption that the ground entropy changes for the two reactions [Eqs. (2) and (3)] are equal. This assumption is reasonable. As well known, the ground entropy change is different from the activation entropy change, activation entropy change is defined as the difference of entropy between reactants and the activation complex, but the ground entropy change is defined as the difference of entropy between reactants and products. It is evident that the activation entropy change for the reaction of the 1,2-dihydronicotinamide with the substrate should be quite larger than that for the reaction of the 1,4-dihydronicotinamide with the substrate; the reason is that there is a larger steric barriers in the activation complex for the former reaction. But as to the ground entropy changes for the two reactions, there should not be remarkable difference between them, since the two reactions give the same products and formation entropies for the two dihydropyridines are close to each other.
48. Here we used reaction enthalpy to take place of Gibbs free energy to predict the spontaneity of the reactions, since standard ground entropy change for the hydride transfer is generally quite small.
49. Some other reduction characters of pyridinium derivatives to yield the corresponding 1,4-dihydropyridines as the major product by hydride transfer have been demonstrated by Kreevoy and co-workers: a) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 2001, 123, 7492; b) I.-S. H. Lee, K.-H. Chow, M. M. Kreevoy, J. Am. Chem. Soc. 2002, 124, 7755; c) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 1997, 119, 2722.
50. Some other reduction characters of pyridinium derivatives to yield the corresponding 1,4-dihydropyridines as the major product by hydride transfer have been demonstrated by Kreevoy and co-workers: a) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 2001, 123, 7492; b) I.-S. H. Lee, K.-H. Chow, M. M. Kreevoy, J. Am. Chem. Soc. 2002, 124, 7755; c) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 1997, 119, 2722.
51. Some other reduction characters of pyridinium derivatives to yield the corresponding 1,4-dihydropyridines as the major product by hydride transfer have been demonstrated by Kreevoy and co-workers: a) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 2001, 123, 7492; b) I.-S. H. Lee, K.-H. Chow, M. M. Kreevoy, J. Am. Chem. Soc. 2002, 124, 7755; c) I.-S. H. Lee, E. H. Jeoung, M. M. Kreevoy, J. Am. Chem. Soc. 1997, 119, 2722.
52. - to yield the 1,4-dihydropyridines is very fast.
53. According to Hammett equation log K = ρσ and ΔH ≈ - RTlog K, the line slope of ΔH against a should be approximately equal to -5.7p.
54. X.-Q. Zhu, Q. Li, W.-F. Hao, J.-P. Cheng, J. Am. Chem. Soc. 2002, 124, 9887.
55. J. W. Buting, S. Sindhuatmadja, J. Org. Chem. 1980, 45, 5411.
56. In fact, similar evaluations of effective charge distribution on an active atom in a transition-state structure by using Hammett linear free-energy relationship were extensively reported in literature: a) M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 3, pp. 52-79; b) A. Williams, Acc. Chem. Res. 1984, 17, 425; c) A. Williams, Acc. Chem. Res. 1989, 22, 387; d) A. Williams, Adv. Phys. Org. Chem. 1991, 27, 1; e) A. Williams, J. Am. Chem. Soc. 1985, 107, 6335.
57. In fact, similar evaluations of effective charge distribution on an active atom in a transition-state structure by using Hammett linear free-energy relationship were extensively reported in literature: a) M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 3, pp. 52-79; b) A. Williams, Acc. Chem. Res. 1984, 17, 425; c) A. Williams, Acc. Chem. Res. 1989, 22, 387; d) A. Williams, Adv. Phys. Org. Chem. 1991, 27, 1; e) A. Williams, J. Am. Chem. Soc. 1985, 107, 6335.
58. In fact, similar evaluations of effective charge distribution on an active atom in a transition-state structure by using Hammett linear free-energy relationship were extensively reported in literature: a) M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 3, pp. 52-79; b) A. Williams, Acc. Chem. Res. 1984, 17, 425; c) A. Williams, Acc. Chem. Res. 1989, 22, 387; d) A. Williams, Adv. Phys. Org. Chem. 1991, 27, 1; e) A. Williams, J. Am. Chem. Soc. 1985, 107, 6335.
59. In fact, similar evaluations of effective charge distribution on an active atom in a transition-state structure by using Hammett linear free-energy relationship were extensively reported in literature: a) M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 3, pp. 52-79; b) A. Williams, Acc. Chem. Res. 1984, 17, 425; c) A. Williams, Acc. Chem. Res. 1989, 22, 387; d) A. Williams, Adv. Phys. Org. Chem. 1991, 27, 1; e) A. Williams, J. Am. Chem. Soc. 1985, 107, 6335.
60. In fact, similar evaluations of effective charge distribution on an active atom in a transition-state structure by using Hammett linear free-energy relationship were extensively reported in literature: a) M. Page, A. Williams, Organic and Bio-organic Mechanism, Addison Wesley Longman, 1997, Chapter 3, pp. 52-79; b) A. Williams, Acc. Chem. Res. 1984, 17, 425; c) A. Williams, Acc. Chem. Res. 1989, 22, 387; d) A. Williams, Adv. Phys. Org. Chem. 1991, 27, 1; e) A. Williams, J. Am. Chem. Soc. 1985, 107, 6335.
61. N. S. Isaacs, Physical Organic Chemistry, 1st ed., Wiley, New York, 1987, Chapter 2.
62. M. Atkinson, R. Marton, R. Naylor, J. Chem. Soc. 1965, 610.
63. T. Zincke, Ann. 1903, 330, 361.
64. a) J. Zablicky, J. Chem. Soc. 1961, 686;
65. b) P. Kolsaker, P. O. Ellingsen, Acta Chem. Scand. B 1979, 33, 138.
66. R. M. G. Robers, D. Ostovic, M. M. Kreevoy, Faraday Diss. Chem. Soc. 1982, 74, 257.
67. F. T. Gucker, H. B. Pickard, R. W. Planck, J. Am. Chem. Soc. 1939, 61, 459.
68. X.-Q. Zhu, J.-Q. He, Q. Li, M. Xian, J. Lu, J.-P. Cheng, J. Org. Chem. 2000, 65, 6729.