Hoogsteen vs. Watson-Crick base pairing: Incorporation of 2-substituted adenine- and 7-deazaadenine 2 `-deoxy-beta-d-ribonucleosides into oligonucleotides
Autor(en): | Ramzaeva, Natalya Michalek, Elisabeth Kazimierczuk, Zygmunt Seela, Frank Rosemeyer, Helmut |
Stichwörter: | 2-CHLORO-2'-DEOXYADENOSINE 5'-TRIPHOSPHATE; B-DNA DODECAMER; Biochemistry & Molecular Biology; Chemistry; Chemistry, Multidisciplinary; DEOXYADENOSINE ANALOGS; DEOXYCYTIDINE KINASE; DUPLEX STABILIZATION; MOLECULAR-STRUCTURE; PHOTOCHEMICAL CONVERSION; PROTECTING GROUPS; SODIUM-SALT GLYCOSYLATION; TRIPLE-HELIX | Erscheinungsdatum: | 2007 | Herausgeber: | WILEY-V C H VERLAG GMBH | Journal: | CHEMISTRY & BIODIVERSITY | Volumen: | 4 | Ausgabe: | 12 | Startseite: | 2725 | Seitenende: | 2744 | Zusammenfassung: | Various 2-substituted 2'-deoxyadenosines and 7-deazaadenosines have been synthesized. The phosphonate building block 9 of 2-chloro-7-deaza-2'-deoxyadenosine (7-deazacladribine; 2) was prepared by 4,4'-dimethoxytritylation of the parent nucleoside (-> 7), followed by protection of the amino function with a formamidine residue (-> 8). The latter was reacted with PCl3/N-methylmorpholine/1,2,4-triazole to give compound 9. Moreover, 2-methoxy-2'-deoxyadenosine (2'-deoxyspongosine; 1b) was converted into the fully protected derivative 12, which was then transformed into the 2-cyanoethyl phosphoramidite 14. Also the 2-(trifluoromethyl)-substituted 2'-deoxyadenosines 19-21 were prepared by glycosylation of the chromophore 16 with the halogenose 17, followed by one-pot deprotection and nucleophilic displacement of the 6-Cl substituent. The new DNA building blocks 9 and 14 were used - together with formerly prepared cladribine derivative 4 - for solid-phase synthesis of a series of oligodeoxyribonucleotides. These were studied with respect to their thermal stability as well as of the base pairing mode (Watson-Crick vs. Hoogsteen) of modified bases. |
ISSN: | 16121872 | DOI: | 10.1002/cbdv.200790222 |
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