Ferrocene–Carbohydrate Conjugates as Electrochemical Probes for Molecular Recognition Studies

Abstract

We report two methods that have allowed the attachment of glucose, mannose and lactose to one or both of the cyclopentadienyl rings of ferrocene. The resulting ferrocene-carbohydrate conjugates were synthesised by the reaction of thioglycosides with ferrocenemethanol and 1,1'-ferrocenedimethanol in acidic media. A second method based on the regiospecific copper(I)-catalysed cycloaddition of propargyl glycoside, azidomethyl and bis(azidomethyl)ferrocene as well as azidoethyl glycoside and ethynylferrocene was also used and led to the synthesis of 1,2,3-triazole-containing glycoconjugates. The electrochemical behaviour of the synthesised glycoconjugates was investigated. In addition, their binding interactions with beta-cyclodextrin were studied by means of NMR spectroscopy, isothermal titration calorimetry, and cyclic and differential pulse voltammetric experiments. These techniques allowed the determination of the thermodynamic parameters of the complexes, the stability constants for the complexes formed with both the neutral and the oxidised states of the ferrocenyl glycoconjugates, the mode of inclusion and the diffusion coefficients for both the glycoconjugates and the complexes.

Ferrocene–β‐Cyclodextrin Conjugates: Synthesis, Supramolecular Behavior, and Use as Electrochemical Sensors

“…Therefore, the K dim value obtained from ITC reflects the competition between the intra‐ and intermolecular self‐inclusion processes. The comparison of the thermodynamic data for 4 with those reported for the binding of conjugate analog 6 to native β‐CD (Table 1, Figure 3)22b suggests that the formation of the dimeric complex gives a more negative Δ H value than that given by the model complex. This is most likely due to the interpenetration of the Fc moieties into the facing hydrophobic CD cavities and thus supports the structure of the dimeric complex proposed above (see Scheme ).…”

A ferrocene redox-active triazolium macrocycle that binds and senses chloride

“…The CuAAC reaction of ferrocene bis(azide) 1 [12], with a large excess of 1,6-heptadiyne afforded 2 in 50% yield. An intramolecular Eglinton cyclisation reaction was used to prepare the ferrocene bis(triazole) macrocycle 3 , in surprisingly good yield (54%) after purification by column chromatography, as well as a small amount (12%) of the corresponding larger tetra(triazole) macrocycle, 4 (Scheme 1).…”

“…Bis(azide) 1 [12], and TBTA [18] were prepared as described in the literature. Dry dichloromethane and acetonitrile were purged with nitrogen and passed through a MBraun MSP-800 column.…”

10 Years of Click Chemistry: Synthesis and Applications of Ferrocene‐Derived Triazoles

“…Likewise, various mono-and bivalent propargylated disaccharides were conjugated to ferrocene by using a copper-catalyzed click reaction to furnish 15 and 16 in good yields. [10] Electrochemical characterization was carried out for all these compounds in water. The half-wave potentials for compounds 7 and 8 were found to be significantly unperturbed among various monovalent glycoside derivatives studied.…”