Metal ion‑promoted cleavage of nucleoside diphosphosugars: a model for reactions of phosphodiester bonds in carbohydrates




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

PublisherSpringer

2015

Journal of Biological Inorganic Chemistry

JBIC

20

8

1299

1306

8

0949-8257

DOIhttps://doi.org/10.1007/s00775-015-1308-9



 Cleavage  of  five  different  nucleoside  diphos-

phosugars  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  transesterifica -

tion 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 + com-

plexes are able to promote a nucleophilic attack of an exter-

nal nucleophile, e.g. a water molecule or metal ion coor-

dinated HO ligand, on phosphate. With the Zn 2 + complex,

this was not observed.




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