Total synthesis of 2',3',4',5',5' '-(2)h(5)-ribonucleosides: the key building blocks for NMR structure elucidation of large RNA.
The diastereospecific chemical syntheses of uridine-2',3',4',5',5' '-(2)H(5) (21a), adenosine-2',3',4',5',5' '-(2)H(5) (21b), cytidine-2',3',4',5',5' '-(2)H(5)(2)H(5) (21c), and guanosine-2',3',4',5',5' '-(2)H(5) (21d) (>97 atom % (2)H at C2', C3', C4', and C5'/C5' ') have been achieved for their use in the solution NMR structure determination of oligo-RNA by the Uppsala "NMR-window" concept (refs 4a-c, 5a, 6), in which a small (1)H segment is NMR-visible, while the rest is made NMR-invisible by incorporation of the deuterated blocks 21a-d. The deuterated ribonucleosides 21a-d have been prepared by the condensation of appropriately protected aglycone with 1-O-acetyl-2,3,5-tri-O-(4-toluoyl)-alpha/beta-D-ribofuranose-2,3,4,5,5'-(2)H(5) (19), which has been obtained via diastereospecific deuterium incorporation at the C2 center of appropriate D-ribose-(2)H(4) derivatives either through an oxidation-reduction-inversion sequence or a one-step deuterium-proton exchange in high overall yield (44% and 24%, respectively).
Földesi
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Department of Bioorganic Chemistry, Box 581, Biomedical Centre, University of Uppsala, SE-751 23 Uppsala, Sweden.
Trifonova
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Dinya
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Chattopadhyaya
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D003903:Deuterium / Q000138:chemical synthesis*; D015335:Molecular Probes / Q000138:chemical synthesis; D019906:Nuclear Magnetic Resonance, Biomolecular; D012313:RNA / Q000737:chemistry; D012263:Ribonucleosides / Q000138:chemical synthesis*; D013237:Stereoisomerism
D015335:Molecular Probes; D012263:Ribonucleosides; D012313:RNA; D003903:Deuterium