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Ferrocenyl GNA Nucleosides: A Bridge between Organic and Organometallic Xeno‐nucleic Acids
Author(s) -
Skiba Joanna,
Yuan Qing,
Hildebrandt Alexander,
Lang Heinrich,
Trzybiński Damian,
Woźniak Krzysztof,
Balogh Ria K.,
Gyurcsik Béla,
Vrček Valerije,
Kowalski Konrad
Publication year - 2018
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201700551
Subject(s) - chemistry , enantiomer , redox , ferrocene , cyclic voltammetry , circular dichroism , enantiomeric excess , enantioselective synthesis , stereochemistry , electrochemistry , metallocene , yield (engineering) , crystallography , medicinal chemistry , organic chemistry , catalysis , electrode , polymerization , polymer , materials science , metallurgy
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‐( N 1‐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.