Metal–ion promoted cleavage of nucleoside diphosphosugars: A model for reactions of phosphodiester bonds in carbohydrates

Dano, Meisa; Elmeranta, Marjukka; Hodgson, David R.W.; Jaakkola, Juho; Korhonen, Heidi; Mikkola, Satu

Abstract

Cleavage of five different nucleoside diphosphosugars has been studied in the presence of Cu2+ and Zn2+ complexes. The results show that metal ion catalysts promote the cleavage via intramolecular transesterification whenever a neighbouring HO group can adopt a cis-orientation with respect to the phosphate. The HO group attacks the phosphate and two monophosphate products are formed. If such a nucleophile is not available, Cu2+ complexes are able to promote a nucleophilic attack of an external nucleophile, e.g. a water molecule or metal ion coordinated HO ligand, on phosphate. With the Zn2+ complex, this was not observed.

Citation

Dano, M., Elmeranta, M., Hodgson, D. R., Jaakkola, J., Korhonen, H., & Mikkola, S. (2015). Metal–ion promoted cleavage of nucleoside diphosphosugars: A model for reactions of phosphodiester bonds in carbohydrates. JBIC Journal of Biological Inorganic Chemistry, 20(8), 1299-1306. https://doi.org/10.1007/s00775-015-1308-9

• Journal Article Type: Article
• Acceptance Date: Oct 23, 2015
• Online Publication Date: Nov 7, 2015
• Publication Date: Dec 1, 2015
• Deposit Date: Oct 30, 2015
• Publicly Available Date: Nov 7, 2016
• Journal: JBIC Journal of Biological Inorganic Chemistry
• Print ISSN: 0949-8257
• Electronic ISSN: 1432-1327
• Publisher: Springer
• Peer Reviewed: Peer Reviewed
• Volume: 20
• Issue: 8
• Pages: 1299-1306
• DOI: https://doi.org/10.1007/s00775-015-1308-9
• Keywords: Carbohydrates, Phosphodiesters, Cleavage, Mechanisms, Metal ion catalysts.