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

A Sharpless asymmetric dihydroxylation reaction was applied to obtain ferrocenyl-GNA nucleosides. These are the first known representatives of redox active organometallic GNA ever reported and contribute to the expanding of GNA family tree. The (S, R) and (R, S) absolute configuration of the chiral carbon atoms in the Fc-GNA nucleosides was assigned by the X-ray crystallography of the methylated derivatives. Furthermore, CD spectroscopy of the methylated derivatives was conducted. The CD spectra are mirror-like images, reflecting the enantiomeric relationship between the compounds. Electrochemical studies reveal that each of the Fc-GNA nucleosides undergoes a reversible one-electron oxidation at a potential of -25 mV (for non-methylated derivatives) and 75 mV (for methylated derivatives), respectively. Further studies are needed to probe the usefulness of the herein reported Fc-GNA nucleosides as building blocks for oligonucleotide synthesis.