Transition-State Effects in the Divalent Metal Ion Catalysis of Acetal Hydrolysis

Journal of the American Chemical Society

Volumn 102, Issue 13, 1980, Pages 4391-4396

  Przystas, Theodore J ^a   Fife, Thomas H ^a  

^a UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33847085272     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00533a017     Document Type: Article

References (31)

1. Postdoctoral Fellow, Department of Biochemistry, University of Southern California.
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20. 2O at high concentrations of Cu 2+ the absorbance increased, which could be due to breakdown of a hemiacetal. This was not observed with the other metal ions, in 50% dioxane-H2O, nor in any of the reactions of III. Therefore, it was not investigated further.
21. De, N. C.; Fedor, L. R. J. Am. Chem. Soc. 1968, 90, 7266.
22. Since this concentration of metal ion is not saturating, larger rate enhancements could be obtained by increasing the metal ion concentration. Also, since the metal ion catalyzed reaction is pH independent, larger enhancements would be observed at higher pH values.
23. Fife, T. H.; Przystas, T. J., unpublished data.
24. Values of the logarithms of the stability constants at 25 °C for complexation of various metal ions with 8-hydroxyquinoline; Cu(ll), 12.10; Ni(ll), 9.27; Co(ll) 8.65; Zn(ll) 8.52; Mn(ll) 6.80. Sillen, L. G.; Martell, A. E. “Stability Constants of Metal-lon Complexes”; The Chemical Society: London, 1964; unpublished data. Supplement No. 1, 1971.
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28. Huber, R. E.; Parfett, C.; Wouife-Flanagan, H.; Thompson, D. J. Biochemistry 1979, 18, 4090.
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30. Bruice, T. C.; Benkovic, S. J. “Bioorganic Mechanisms;” W. A. Benjamin: New York, 1966.
31. The rate enhancements produced in the metal ion catalyzed hydrolysis reactions by substitution of a carboxyl group into the 2 position are much greater with the ester 8-(2-carboxyquinolyl) hydrogen glutarate and show a larger variation within the series of metal ions than in the case of the acetal III. This difference arises because of the different mechanisms, the ester hydrolyzing with metal ion promoted attack of OH at the ester carbonyl.