Synthesis and characterization of ferrocene-labeled oligodeoxynucleotides

Conformationally Gated Electrochemical Gene Detection

“…[17] The modified DNA (Fc-hairpin-SH) was synthesized by modifying the CPG resin with a C 6 -thiol linker (Glen Research). The 5' end was modified with ferrocenyl phosphoramidite by using the method previously described by Mirkin and co-workers.…”

“…Ferrocene was chosen as the electroactive probe in these studies because of its proven utility in biological diagnostics, [9,14,15] its stability during DNA synthesis, [16,17] and its accessible redox potential under physiological conditions. To afford significant structural rearrangement of the electroactive DNA, we selected a DNA stem-loop sequence, with the loop DNA sequence complementary to a specific DNA target.…”

Metal–Carbon Bonds in Biopolymer Conjugates: Bioorganometallic Nucleic Acid Chemistry

“…38 Ferrocene tags containing amide linkers similar to those in Figure 1 have also been incorporated using this methodology. 23 However, with significant advances in the synthesis of ferrocene derivatives, there are a number of examples of ferrocenyl nucleosides being prepared for internal incorporation into oligonucleotides via phosphoramidite chemistry. Early examples involved uridines and adenosine being functionalized with ferrocenes via single, double, and triple bonds using palladiumcatalyzed cross-coupling reactions.…”

“…41 Ferrocene has also been introduced at the 5¤-and 8-positions of adenosine 42 and in both the 5¤-and 5-positions of uridine. 23 Houlton and co-workers have attached ferrocene to the 5-position of thymidine via single, double, and, again unsuccessfully, triple bonds. 43 They successfully functionalized cytidine 10 using the same methodology and attached the resulting strand to a silicon surface.…”

“…The Sonogashira reaction has been used to react solidbound oligonucleotides containing iodouridine (5-IdU) or bromoadenosine (8-BrdA) with a propargylamine-functionalized ferrocene 4 ( Figure 2). 23,24 Recently, click chemistry has been used to add multiple ferrocene moieties to DNA at both the 5¤-position 5 25 and the backbone, with the latter approach yielding up to five adjacent ferrocenes. 26 A more unusual example of the postsynthetic incorporation of an organometallic moiety into DNA was shown by Jäschke and co-workers, 27 whose DNA dieneiridium(I) system was shown to enantioselectively catalyze allylic amination reactions.…”