A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
There is no universal mechanism for the cleavage of RNA model compounds in the presence of metal ion catalysts
Tekijät: Korhonen H, Koivusalo T, Toivola S, Mikkola S
Kustantaja: ROYAL SOC CHEMISTRY
Julkaisuvuosi: 2013
Journal: Organic and Biomolecular Chemistry
Tietokannassa oleva lehden nimi: ORGANIC & BIOMOLECULAR CHEMISTRY
Lehden akronyymi: ORG BIOMOL CHEM
Numero sarjassa: 48
Vuosikerta: 11
Numero: 48
Aloitussivu: 8324
Lopetussivu: 8339
Sivujen määrä: 16
ISSN: 1477-0520
DOI: https://doi.org/10.1039/c3ob41554f
Tiivistelmä
The transesterification of uridine 3'-phosphodiesters with a wide range of leaving group alcohols has been studied in the presence of monometallic and bimetallic complexes. The catalysis of isomerization of the phosphodiester bond was studied with a nucleoside 3'-phosphonate as a substrate. The results obtained are consistent with a step-wise mechanism, where metal ions are able to enhance both the nucleophilic attack and the departure of the leaving group. The mechanism of the catalysis depends on the acidity of the catalyst and of the leaving group alcohol: a change from general base catalysis to general acid catalysis is proposed. Catalysis of the isomerization requires efficient stabilization of the phosphorane by strong interactions with the catalyst. Catalytic strategies utilised by bimetallic complexes are also briefly discussed.
The transesterification of uridine 3'-phosphodiesters with a wide range of leaving group alcohols has been studied in the presence of monometallic and bimetallic complexes. The catalysis of isomerization of the phosphodiester bond was studied with a nucleoside 3'-phosphonate as a substrate. The results obtained are consistent with a step-wise mechanism, where metal ions are able to enhance both the nucleophilic attack and the departure of the leaving group. The mechanism of the catalysis depends on the acidity of the catalyst and of the leaving group alcohol: a change from general base catalysis to general acid catalysis is proposed. Catalysis of the isomerization requires efficient stabilization of the phosphorane by strong interactions with the catalyst. Catalytic strategies utilised by bimetallic complexes are also briefly discussed.
Turun yliopiston Tutkimustietojärjestelmän portaali