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Volumn 74, Issue 1, 2009, Pages 144-152

Kinetic mechanism and structural requirements of the amine-catalyzed decarboxylation of oxaloacetic acid

Author keywords

[No Author keywords available]

Indexed keywords

AMINO GROUPS; CARBINOLAMINE DEHYDRATIONS; CATALYTIC MECHANISMS; CHEMICAL EQUATIONS; CHEMICAL MECHANISMS; DI-AMINES; ELECTRONIC REQUIREMENTS; ENAMINE TAUTOMERS; IMINE FORMATIONS; IMINE INTERMEDIATES; KINETIC MECHANISMS; MALATE DEHYDROGENASES; NEGATIVE CHARGES; PROTON SHUTTLES; PYRUVATE; REACTIVE IMINES; STRUCTURAL REQUIREMENTS;

EID: 58149296144     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8014648     Document Type: Article
Times cited : (17)

References (53)
  • 21
    • 58149308937 scopus 로고    scopus 로고
    • An analogous mechanism has also been proposed for amine catalyzed decarboxylation of acetoacetate, another β-ketocarboxylic acid. 10
    • 10
  • 25
    • 58149294131 scopus 로고    scopus 로고
    • McMurry, J.; Begley, T. The Organic Chemistry of Biological Pathways; Roberts and Company: Englewood, CO, 2005; 172-173, 208-210, 223-226.
    • McMurry, J.; Begley, T. The Organic Chemistry of Biological Pathways; Roberts and Company: Englewood, CO, 2005; 172-173, 208-210, 223-226.
  • 39
    • 58149303377 scopus 로고    scopus 로고
    • 21 Lastly, control experiments in HEPES buffer showed that while Tris is an amine it did not react with oxaloacetate, whereas ethylenediamine did.
    • 21 Lastly, control experiments in HEPES buffer showed that while Tris is an amine it did not react with oxaloacetate, whereas ethylenediamine did.
  • 41
    • 58149300325 scopus 로고    scopus 로고
    • Two other assays were used to confirm that pyruvate was indeed being produced by the decarboxylation reaction. NMR analysis confirmed the product was pyruvate, but the rates of decarboxylation could not be compared to the assay used here because the analysis was performed in DMSO. In addition, lactate dehydrogenase also detected the production of pyruvate. However, the very low concentrations of oxaloacetate used in the malate dehydrogenase assay were not feasible for the lactate dehydrogenase assay and thus the rates from the two assays cannot be compared directly, which underscores the sensitivity as well as the versatility of the malate dehydrogenase assay used in this study
    • Two other assays were used to confirm that pyruvate was indeed being produced by the decarboxylation reaction. NMR analysis confirmed the product was pyruvate, but the rates of decarboxylation could not be compared to the assay used here because the analysis was performed in DMSO. In addition, lactate dehydrogenase also detected the production of pyruvate. However, the very low concentrations of oxaloacetate used in the malate dehydrogenase assay were not feasible for the lactate dehydrogenase assay and thus the rates from the two assays cannot be compared directly, which underscores the sensitivity as well as the versatility of the malate dehydrogenase assay used in this study.
  • 42
    • 58149286673 scopus 로고    scopus 로고
    • 24
    • 24
  • 47
    • 58149288744 scopus 로고    scopus 로고
    • A helpful reviewer has pointed out that the lack of reactivity of aniline and aminoacetonitrile could also be the consequence of unfavorably low equilibrium constants for imine formation at pH 8.0
    • A helpful reviewer has pointed out that the lack of reactivity of aniline and aminoacetonitrile could also be the consequence of unfavorably low equilibrium constants for imine formation at pH 8.0.
  • 49
    • 58149294122 scopus 로고    scopus 로고
    • In addition to enamine tautomerization, other possible unreactive intermediates include imidazolidines (from ring-closing with diamines, thiazolidines (from cysteamine ring-closing, and oxazolidines (from ethanolamine ring-closing, The formation of these intermediates would decrease catalytic rates in much the same way as enamine tautomerization. However, imizadolidine formation does not appear to be as significant as enamine tautomerization in diamine-catalyzed decarboxylation because, otherwise, increasing diamine chain length (which would decrease the stability of the corresponding unreactive cyclic intermediates) would have resulted in increased rates of decarboxylation. On the other hand, thiazolidine and oxazolidine ring-closing may be significant factors in the low decarboxylation rates observed for cysteamine and ethanolamine
    • In addition to enamine tautomerization, other possible unreactive intermediates include imidazolidines (from ring-closing with diamines), thiazolidines (from cysteamine ring-closing), and oxazolidines (from ethanolamine ring-closing). The formation of these intermediates would decrease catalytic rates in much the same way as enamine tautomerization. However, imizadolidine formation does not appear to be as significant as enamine tautomerization in diamine-catalyzed decarboxylation because, otherwise, increasing diamine chain length (which would decrease the stability of the corresponding unreactive cyclic intermediates) would have resulted in increased rates of decarboxylation. On the other hand, thiazolidine and oxazolidine ring-closing may be significant factors in the low decarboxylation rates observed for cysteamine and ethanolamine.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.