On-column derivatization of oligodeoxynucleotides with ferrocene

Abstract

The solid-phase synthesis and characteristics of ferrocenoyl propargylamide (FPA)-labeled oligodeoxynucleotides are described.

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

“…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.…”

Synthesis of β‐Pyrrolic‐Modified Porphyrins and Their Incorporation into DNA

“…Previously, the palladium(0)-catalysed Sonogashira reaction was performed on a solid support of ONs possessing 5-iodopyrimidines, [38] 8-bromopurines [39] as well as 2-or 4-iodobenzyl-or 4-ethynylbenzylglycerols. [28,40] No side-reactions were observed for native nucleobases with protecting groups.…”

“…[28,40] No side-reactions were observed for native nucleobases with protecting groups. [38] For the post-synthetic Sonogashira reaction using automated DNA synthesis we prepared 5'-DMT-on ONs ON1-ON3 containing a single internal insertion of one of the following functionalised DNA building blocks: 2'-deoxy-5-ethynyluridine (V; Scheme 1), 2'-deoxy-8-bromoguanosine (W) or (R)-1-O-(2-iodobenzyl)glycerol (X; Scheme 4). The phosphoramidites required for oligonucleotide synthesis were either prepared, as in the case of 2'-deoxy-5-ethynyl- [26] and (R)-1-O-(2-iodobenzyl)glycerol, [28] or purchased, as in the case of 8-bromo-2'-deoxyguanosine.…”

Functional Electroactive Biomolecules

“…Houlton and coworkers 84 reinvestigated this reaction and it was reported that it is possible to suppress the cyclization by running the Sonogashira reaction at room temperature for 4 h. Houlton and coworkers 85 also made use of trimethylammoniummethylferrocene iodide as a source of the ferrocenemethyl cation to form Fc-nucleobase conjugates. 86,87 A Sonagashira cross-coupling reaction, using Pd(PPh 3 ) 4 and CuI, links Fc propargylamide to a halogenated base, such as 2 0 -deoxy-5-iodouridine or 8-bromo-2 0 -deoxyadenosine, which has been previously incorporated in the ODN strand (see Scheme 10.2). Figure 10.11 shows the structure of 1-ferrocenylmethylcytosine.…”