New Approaches toward Ferrocene–Guanine Conjugates: Synthesis and Electrochemical Behavior

Iurlo, Matteo; Mengozzi, Luca; Rapino, Stefania; Marcaccio, Massimo; Perone, Rosaria Carmela; Masiero, Stefano; Cozzi, Pier Giorgio; Paolucci, Francesco

doi:10.1021/om5002809

Cited by 16 publications

(12 citation statements)

References 45 publications

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“…Keeping in mind potential applications of the redox‐active XNA, the ferrocenyl–nucleobase conjugates, and the ferrocenyl nucleosides, the electrochemical behavior of compounds 1 – 5 was investigated by means of cyclic voltammetry (CV). The electrochemical measurements were carried out in an atmosphere of argon using a solution of anhydrous dimethyl sulfoxide (DMSO) that contained weakly coordinating [Bu 4 N][B(C 6 F 5 ) 4 ] (0.1 mol L −1 ) as supporting electrolyte .…”

Section: Resultsmentioning

confidence: 99%

1,1′‐Bis(thymine)ferrocene Nucleoside: Synthesis and Study of Its Stereoselective Formation

et al. 2017

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The synthesis of 1,1′‐bis(thymine)ferrocene nucleoside is reported. This nucleoside was obtained in a two‐step synthetic methodology including a Michael addition reaction of 1,1′‐bis(3‐chloropropionyl)ferrocene with thymine to afford the bis(thymine) adduct in 44 % yield. In the second step, the two prochiral carbonyl functionalities in the Michael adduct were reduced to hydroxyl groups with sodium borohydride. This apparently straightforward reaction proceeds in a highly stereoselective fashion to yield the title ferrocenyl nucleoside as a racemic mixture that consists of the R,R and the S,S isomers. The absolute configuration of the chiral carbon atoms in the nucleoside was assigned on the basis of single‐crystal X‐ray diffraction analysis of the methyl derivative. Furthermore, the mechanism of reduction of the bis(thymine) adduct was investigated by using DFT calculations. The two critical minima, pre‐reactive complex, and semi‐reduced intermediate, as well as two corresponding transition states were located to support the observed stereoselectivity. The redox properties of 1,1′‐bis(thymine)ferrocene nucleoside, its precursor, and congeners were investigated using cyclic voltammetry. For the title compound a reversible redox process was found at a low potential of −30 mV versus FcH/FcH+ (FcH=Fe(η5‐C5H5)2) as the reference redox couple.

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Section: Resultsmentioning

confidence: 99%

1,1′‐Bis(thymine)ferrocene Nucleoside: Synthesis and Study of Its Stereoselective Formation

et al. 2017

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“…Ferrocenyl XNA nucleotides have been utilized as building blocks for construction of short redox‐active nucleic acid strands and ferrocenyl guanine conjugates have been used as standards for the quantification and analysis of DNA strands . Furthermore, it has been shown that specifically designed, chelating oligonucleotides can self‐assemble into metal‐mediated nanowire structures .…”

Section: Resultsmentioning

confidence: 99%

Ferrocenyl GNA Nucleosides: A Bridge between Organic and Organometallic Xeno‐nucleic Acids

et al. 2018

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The enantioselective synthesis and electrochemistry of the first ferrocenyl GNA nucleosides is reported. These compounds were obtained by a Sharpless asymmetric dihydroxylation reaction of [3‐(N1‐thyminyl)‐1‐(ferrocenyl)]propene as S,R and R,S enantiomers in about 70 % yield with enantiomeric excesses of >99 % and 71 %, respectively. The absolute configurations of the chiral carbon atoms in the nucleosides were assigned by single‐crystal X‐ray diffraction analysis of the methyl derivatives in the solid state. The compounds were also studied with circular dichroism (CD) spectroscopy in solution. The enantiomeric relationship between the S,R and R,S isomers was confirmed by the near‐mirror‐image CD spectra. The redox properties of the nucleosides and their methylated derivatives were investigated using cyclic voltammetry. The cyclic voltammograms revealed reversible redox processes for the entire series of compounds at potentials of −25 mV (for nonmethylated derivatives) and 75 mV (for methylated derivatives) versus the ferrocene/ferrocenium reference redox couple.

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“…Decamethylferrocene was used as an internal standard at the end of every measurement. Details have been provided elsewhere . Cyclic voltammetry of Salophen complexes spin‐coated on HOPG was performed in a standard three‐electrode electrochemical cell, in which Ag/AgCl, KCl (3 m ) was the reference electrode, Pt spiral is the counter and HOPG acts as working electrode.…”

Section: Methodsmentioning

confidence: 99%

“…Details have been provided elsewhere. [38] Cyclic voltammetry of Salophen complexes spin-coated on HOPG was performed in as tandard three-electrode electrochemical cell, in which Ag/AgCl, KCl (3 m)w as the reference electrode, Pt spiral is the counter and HOPG acts as working electrode. Measurements were carried out in distilled water with KCl 0.1 m as supporting electrolyte.…”

Section: Experimental Section Electrochemistrymentioning

confidence: 99%

Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self‐Assembly at Surfaces of Multifunctional Systems

Mengozzi

Garah

Gualandi

et al. 2018

Chemistry A European J

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Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2-phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self-assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air-stable [Al(Salophen)] derivatives capable of undergoing spontaneous self-assembly at the graphite/solution interface forming highly-ordered nanopatterns. The new synthetic approach relies on the use of [MeAl (Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five-coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self-assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.

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New Approaches toward Ferrocene–Guanine Conjugates: Synthesis and Electrochemical Behavior

Cited by 16 publications

References 45 publications

1,1′‐Bis(thymine)ferrocene Nucleoside: Synthesis and Study of Its Stereoselective Formation

1,1′‐Bis(thymine)ferrocene Nucleoside: Synthesis and Study of Its Stereoselective Formation

Ferrocenyl GNA Nucleosides: A Bridge between Organic and Organometallic Xeno‐nucleic Acids

Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self‐Assembly at Surfaces of Multifunctional Systems

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