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Volumn 68, Issue 4, 2003, Pages 1529-1538

A repertoire of pyridinium-phenyl-methyl cross-talk through a cascade of intramolecular electrostatic interactions

Author keywords

[No Author keywords available]

Indexed keywords

ALKALINITY; AROMATIZATION; FREE ENERGY; GROUND STATE; TITRATION;

EID: 84961980623     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026572e     Document Type: Article
Times cited : (26)

References (59)
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    • N-P (in ppm) corresponds to the relative shielding (upfield shift, Δδ or ΔΔδ > 0) or deshielding (downfield shift, Δδ or ΔΔδ < 0) as a function of pH.
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    • a perturbation. (b) Ishida, T.; Shibata, M.; Fuji, K.; Inoue, M. Biochemistry 1983, 22, 3571. (c) Schmidt, A.; Kindermann, M. K.; Vainotalo, P.; Nieger, M. J. Org. Chem. 2000, 64, 9499. (d) Cozzi, F.; Cinquini, M.; Annuziata, R.; Dwyer, T.; Siegel, J. S. J. Am. Chem. Soc. 1992, 114, 5729. (e) Guckian, K. M.; Schweitzer, B. A.; Rex, X.F.; Charles, J. S.; Tahmassebi, D. C.; Kool, E. T. J. Am. Chem. Soc. 2000, 122, 2213. (f) Ribas, J.; Cubero, E.; Luque, J.; Orozco, M. J. Org. Chem. 2002, 67, 7057 and references therein. (g) Quiñonero, D.; Garau, C.; Rotger, C.; Frontera, A.; Ballester, P.; Costa, A.; Deyà, P. M. Angew. Chem., Int. Ed. 2002, 41, 3389. (h) Narlikar, G. J.; Herschlag, D. Annu. Rev. Biochem. 1997, 66, 19 and references therein.
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    • note
    • + [because of nonuniform shielding among pyridinyl protons (vide infra) suggesting that H5/H9 edge of pyridinyl moiety is more in contact with the phenyl than the H7/H8 edge] in contrast to the solid-state structure of 1b.
  • 34
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    • note
    • a of pyridine from the pH-dependent chemical shifts of both methyl groups, which shows that the whole pyridine-phenyl-methyl system is indeed coupled-one cross-modulates the other in tandem by using the electrostatic as the engine, and the origin of this electrostatics is a far away point in the molecule-the pyridinyl-nitrogen.
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    • (c) The experimental evidence showed that the magnitude of offset edge-to-face stacking interactions is dictated by the geometry of the stacked components, which, in turn, is influenced by the nature of ring substituents. Kim, E.; Paliwal, S.; Wilcox, C. S. J. Am. Chem. Soc. 1998, 120, 11192.
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    • note
    • 1a+.
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    • NMR Tables, Bruker
    • Bruker Almanac, NMR Tables; Bruker, 1998; p 14.
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