We report the synthesis of pyrene-conjugated azanucleoside-incorporated oligodeoxynucleotides
(aza-ODNs). Combination of liquid-phase synthesis by alkyl-chain-soluble-support (ACSS)
and electrochemical C–H activation realized efficient access to aza-ODNs without requiring
an excess amount of reagent or solvent. The fluorescent properties of pyrene-conjugated
aza-ODNs were also investigated. The resulting fluorescence spectrum indicated that
the modification of the position of the nitrogen atom was suitable for the preparation
of artificial functionalized oligonucleotides. A synthetic route to azaribose, as
a precursor of aza-ODNs, was also reinvestigated to realize more efficient production.
Electrochemical N-α-acetoxylation in 0.1 M lithium perchlorate/nitromethane/50 mM
AcOH medium was found to be a suitable medium for this route. These results represent
a new efficient synthetic route to aza-ODNs.
Key words
electrochemistry - C–H activation - nucleoside - nucleoside analogue - nucleic acid
- acetoxylation Lewis acid