beta-Selective synthesis of 2'-deoxy-5,6-dihydro-4-thiouridine, a precursor of the unstable nucleoside product of ionising radiation damage 2'-deoxy-5,6-dihydrocytidine

4-Thio oxathiaphosphepane nucleosides - undergo a rearrangement in pyridine that leads selectively to the beta anomer of the 2'-deoxy-5,6-dihydro-4-thiouridine derivative . This diastereoselective reaction proceeds through a multistep mechanism initiated by the addition of pyridine at the C1�...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2005-05, Vol.3 (9), p.1685-1689
Main Authors: Peyrane, Frederic, Clivio, Pascale
Format: Article
Language:English
Subjects:
Deoxycytidine - analogs & derivatives
Deoxycytidine - chemistry
Deoxyuridine - analogs & derivatives
Deoxyuridine - chemical synthesis
Magnetic Resonance Spectroscopy
Radiation, Ionizing
Spectrometry, Mass, Electrospray Ionization
Thiouridine - analogs & derivatives
Thiouridine - chemical synthesis
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Summary:4-Thio oxathiaphosphepane nucleosides - undergo a rearrangement in pyridine that leads selectively to the beta anomer of the 2'-deoxy-5,6-dihydro-4-thiouridine derivative . This diastereoselective reaction proceeds through a multistep mechanism initiated by the addition of pyridine at the C1'position of - and concomitant opening of the oxathiaphosphepane. This was confirmed by the trapping of the corresponding intermediate in the closely related DMAP series. In contrast, LR thiation of in pyridine leads to a new class of modified nucleosides containing an oxathiaphospholane moiety. The quantitative conversion of into the corresponding 5,6-dihydrocytosine derivative with NH3-MeOH is also reported.
ISSN:1477-0520
1477-0539
DOI:10.1039/b502302e