文摘
Aqueous-phase Heck coupling methodology was developed for direct attachment of butyl acrylate to 5-iodoracil, 5-iodocytosine, 7-iodo-7-deazaadenine, and 7-iodo-7-deazaguanine 2鈥?deoxyribonucleoside 5鈥?O-monophosphates (dNMPs) and 5鈥?O-triphosphates (dNTPs) and compared with the classical approach of phosphorylation of the corresponding modified nucleosides. The 7-substituted 7-deazapurine nucleotides (dABAMP, dABATP, dGBAMP, and dGBATP) were prepared by the direct Heck coupling of nucleotides in good yields (35鈥?5%), whereas the pyrimidine nucleotides reacted poorly and the corresponding BA-modified dNTPs were prepared by triphosphorylation of the modified nucleosides. The acrylate-modified dNBATPs (N = A, C, and U) were good substrates for DNA polymerases and were used for enzymatic synthesis of acrylate-modified DNA by primer extension, whereas dGBATP was an inhibitor of polymerases. The butyl acrylate group was found to be a useful redox label giving a strong reduction peak at 鈭?.3 to 鈭?.4 V in cyclic voltammetry.