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. 1982 Jul 24;10(14):4339–4349. doi: 10.1093/nar/10.14.4339

Mechanisms for the solvolytic decompositions of nucleoside analogues. X. Acidic hydrolysis of 6-substituted 9-(beta-D-ribofuranosyl)purines.

H Lönnberg, P Lehikoinen
PMCID: PMC320803  PMID: 7122238

Abstract

The pH-rate profiles were determined for the acidic hydrolysis of some 6-substituted 9-(beta-D-ribofuranosyl) purines. The product analyses indicated that the reactions generally proceed with formation of purine bases as initial products. However, at low oxonium ion concentrations the hydrolysis of the unsubstituted compound yields 4-amino-5-formamidopyrimidine, instead of purine formed in highly acidic solutions. The rate constants for the spontaneous and oxonium ion catalyzed heterolysis of the protonated substrates were calculated from the acidity constants and the observed rate constants. The dependence of the partial rate constants on the polar nature of the 6-substituents are consistent with rate-limiting formation of free purine bases and glycosyl oxocarbenium ions. No anomerization of the substrates was observed during the course of the hydrolysis.

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Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Cadet J., Teoule R. Letter: Nucleic acid hydrolysis. I. Isomerization and anomerization of pyrimidic deoxyribonucleosides in an acidic medium. J Am Chem Soc. 1974 Oct 2;96(20):6517–6519. doi: 10.1021/ja00827a047. [DOI] [PubMed] [Google Scholar]
  2. DEKKER C. A. Nucleic acids. Selected topics related to their enzymology and chemistry. Annu Rev Biochem. 1960;29:453–474. doi: 10.1146/annurev.bi.29.070160.002321. [DOI] [PubMed] [Google Scholar]
  3. Garrett E. R., Mehta P. J. Solvolysis of adenine nucleosides. I. Effects of sugars and adenine substituents on acid solvolyses. J Am Chem Soc. 1972 Nov 29;94(24):8532–8541. doi: 10.1021/ja00779a040. [DOI] [PubMed] [Google Scholar]
  4. Hevesi L., Wolfson-Davidson E., Nagy J. B., Nagy O. B., Bruylants A. Contribution to the mechanism of the acid-catalyzed hydrolysis of purine nucleosides. J Am Chem Soc. 1972 Jun 28;94(13):4715–4720. doi: 10.1021/ja00768a046. [DOI] [PubMed] [Google Scholar]
  5. Jordan F., Niv H. Glycosyl conformational and inductive effects on the acid catalysed hydrolysis of purine nucleosides. Nucleic Acids Res. 1977 Mar;4(3):697–709. doi: 10.1093/nar/4.3.697. [DOI] [PMC free article] [PubMed] [Google Scholar]
  6. Shapiro R., Danzig M. Acidic hydrolysis of deoxycytidine and deoxyuridine derivatives. The general mechanism of deoxyribonucleoside hydrolysis. Biochemistry. 1972 Jan 4;11(1):23–29. doi: 10.1021/bi00751a005. [DOI] [PubMed] [Google Scholar]
  7. Shapiro R., Kang S. Uncatalyzed hydrolysis of deoxyuridine, thymidine, and 5-bromodeoxyuridine. Biochemistry. 1969 May;8(5):1806–1810. doi: 10.1021/bi00833a004. [DOI] [PubMed] [Google Scholar]
  8. Zoltewicz J. A., Clark D. F. Kinetics and mechanism of the hydrolysis of guanosine and 7-methylguanosine nucleosides in perchloric acid. J Org Chem. 1972 Apr 21;37(8):1193–1197. doi: 10.1021/jo00973a025. [DOI] [PubMed] [Google Scholar]
  9. Zoltewicz J. A., Clark D. F., Sharpless T. W., Grahe G. Kinetics and mechanism of the acid-catalyzed hydrolysis of some purine nucleosides. J Am Chem Soc. 1970 Mar 25;92(6):1741–1749. doi: 10.1021/ja00709a055. [DOI] [PubMed] [Google Scholar]

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