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Volumn 129, Issue 34, 2007, Pages 10330-10331

A simple method to determine kinetic deuterium isotope effects provides evidence that proton transfer to carbon proceeds over and not through the reaction barrier

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; DEUTERIUM;

EID: 34548250959     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja073679g     Document Type: Article
Times cited : (18)

References (20)
  • 1
    • 34548227922 scopus 로고    scopus 로고
    • Hynes, J. T, Klinman, J. P, Limbach, H.-H, Schowen, R. L, Eds, Wiley-VCH: Weinheim, Germany
    • Kiefer, P. M.; Hynes, J. T. In Hydrogen Transfer Reactions; Hynes, J. T., Klinman, J. P., Limbach, H.-H., Schowen, R. L., Eds.; Wiley-VCH: Weinheim, Germany, 2007; Vol. 1, pp 303-348.
    • (2007) Hydrogen Transfer Reactions , vol.1 , pp. 303-348
    • Kiefer, P.M.1    Hynes, J.T.2
  • 2
    • 34548249672 scopus 로고    scopus 로고
    • Hynes, J. T, Klinman, J. P, Limbach, H.-H, Schowen, R. L, Eds, Wiley-VCH: Weinheim, Germany
    • Williams, I. H. In Hydrogen Transfer Reactions; Hynes, J. T., Klinman, J. P., Limbach, H.-H., Schowen, R. L., Eds.; Wiley-VCH: Weinheim, Germany, 2007; Vol. 2, pp 583-602.
    • (2007) Hydrogen Transfer Reactions , vol.2 , pp. 583-602
    • Williams, I.H.1
  • 6
    • 0004258726 scopus 로고
    • 2nd ed, Cornell University Press: Ithaca, NY
    • Bell, R. P. The Proton in Chemistry, 2nd ed.; Cornell University Press: Ithaca, NY, 1973; pp 250-296.
    • (1973) The Proton in Chemistry , pp. 250-296
    • Bell, R.P.1
  • 11
    • 34548235928 scopus 로고    scopus 로고
    • Reactions were initiated by making a 1/100 dilution of the substrate in acetonitrile into 50/50 (v/v) H2O/D2O (1, 1.0, KCl) to give the following final concentrations and reaction 4-MeO-1, 0.3 mM in 25 mL; 1, 0.8 mM in 10 mL; 4-NO 2-1, 0.09 mM in 50 mL; and, 3,5-di-NO2-1, 0.06 mM in 50 mL. After 5-7 reaction halftimes, the organic product was extracted into CDCl3. The organic layer was dried by filtration through a short column of MgSO4 directly into an NMR tube, and the samples were stored at -15°C until being analyzed for deuterium content by 1H NMR. Control experiments with 3,5-di-NO2-1 were performed to show that the ketone reaction product is stable to base-catalyzed deuterium exchange of the α-methyl protons during acid-catalyzed hydrolysis of 3,5-di-NO2-1
    • 2-1.
  • 12
    • 34548209989 scopus 로고    scopus 로고
    • Each PIE is the average of PIEs determined in five experiments at different acid concentrations
    • (b) Each PIE is the average of PIEs determined in five experiments at different acid concentrations.
  • 13
    • 34548293316 scopus 로고    scopus 로고
    • 2D groups.
    • 2D groups.
  • 17
    • 34548229514 scopus 로고    scopus 로고
    • D) = -0.048 ± 0.11 and -0.001 ± 0.06. The quoted errors are standard deviations.
    • D) = -0.048 ± 0.11 and -0.001 ± 0.06. The quoted errors are standard deviations.
  • 18
    • 85056422813 scopus 로고    scopus 로고
    • Kohen, A, Limbach, H.-H, Eds, Taylor & Francis: New York
    • Kohen, A. In Isotope Effects in Chemistry and Biology; Kohen, A., Limbach, H.-H., Eds.; Taylor & Francis: New York, 2006; pp 743-764.
    • (2006) Isotope Effects in Chemistry and Biology , pp. 743-764
    • Kohen, A.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.