title: Metal ion-promoted cleavage of nucleoside diphosphosugars: a model for reactions of phosphodiester bonds in carbohydrates.
abstract: Cleavage of five different nucleoside diphosphosugars has been studied in the presence of Cu(2+) and Zn(2+) 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, Cu(2+) 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 Zn(2+) complex, this was not observed.
authors.affiliation: Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland.
authors.forename: Meisa
authors.initials: M
authors.lastname: Dano
authors.affiliation: Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland.
authors.forename: Marjukka
authors.initials: M
authors.lastname: Elmeranta
authors.affiliation: Department of Chemistry, University of Durham, Science Labs, South Road, Durham, DH1 3LE, UK.
authors.forename: David R W
authors.initials: DR
authors.lastname: Hodgson
authors.affiliation: Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland.
authors.forename: Juho
authors.initials: J
authors.lastname: Jaakkola
authors.affiliation: Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland.
authors.forename: Heidi
authors.initials: H
authors.lastname: Korhonen
authors.affiliation: Department of Chemistry, University of Turku, Vatselankatu 2, 20014, Turku, Finland. satu.mikkola@utu.fi.
authors.forename: Satu
authors.initials: S
authors.lastname: Mikkola
mesh_terms: D050260:Carbohydrate Metabolism; D002241:Carbohydrates / Q000737:chemistry; D056831:Coordination Complexes / Q000378:metabolism; D003300:Copper / Q000737:chemistry; D007477:Ions / Q000737:chemistry*; D009705:Nucleosides / Q000737:chemistry*; D010755:Organophosphates / Q000737:chemistry; D015032:Zinc / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D056831:Coordination Complexes; D007477:Ions; D009705:Nucleosides; D010755:Organophosphates; D003300:Copper; D015032:Zinc
keywords: Carbohydrates; Cleavage; Mechanisms; Metal ion catalysts; Phosphodiesters