Convenient Methods for the Synthesis of Ferrocene−Carbohydrate Conjugates

Casas‐Solvas, Juan M.; Vargas‐Berenguel, Antonio; Capitán-Vallvey, L.F.; Santoyo‐González, Francisco

doi:10.1021/ol048665j

Cited by 132 publications

(98 citation statements)

References 49 publications

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“…[38] Starting from the sidechain-modified PMMA 33, which bears multiple acetylenic moieties, a number of carbohydrates can be affixed (e.g., 1-azidosugars, 6-azidosugars). In accordance with previous investigations on carbohydrates [39,40] and cyclodextrins [41] the carbohydrates can be either fully protected or, alternatively, can be used in the unprotected state with (Ph 3 ) 3 Cu I Br and diisopropylethylamine (DIPEA) in DMSO as the catalytic system. As an elegant application, the generation of a library of mannose-and galactosecontaining polymers 35 and 36 by a 'co-clicking' approach was reported.…”

Section: Click Reactions On Linear Polymers and Gelsmentioning

confidence: 55%

‘Click’ Chemistry in Polymer and Materials Science

Binder

Sachsenhofer

2007

Macromol. Rapid Commun.

1,480

866

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IntroductionThe azide/alkyne 'click' reaction [1] (also termed the Sharpless 'click' reaction) is a recent re-discovery of a reaction fulfilling many requirements for the affixation of ligands onto polymers by post-modification processes, which include a) often quantitative yields, b) a high tolerance of functional groups, c) an insensitivity of the reaction to solvents, irrespective of their protic/aprotic or polar/ non-polar character, and d) reactions at various types of interfaces, such as solid/liquid, liquid/liquid, or even solid/ solid interfaces. The present review focuses on issues related to the reaction itself as well as on the wide applications in polymer science, material, and surface science.The basic reaction, which is nowadays summed up under the name 'Sharpless-type click reaction', is a variant of the Huisgen 1,3-dipolar cycloaddition reaction [2a,2b] between C-C triple, C-N triple bonds, and alkyl-/aryl-/ sulfonyl azides (see Scheme 1).The relevant outcomes of this reaction are tetrazoles, 1,2,3-triazoles, or 1,2-oxazoles (Scheme 1a-c, respectively). Besides the 1,3-dipolar cycloaddition reaction, classical Diels-Alder-type reactions (Scheme 1d) have been used extensively for the functionalization of polymeric materials and surfaces. [3] These reactions are located within a series of reactions named click reactions, which is defined by a gain of thermodynamic enthalpy of at least 20 kcal Á mol À1 , [1] thus leading to reactions characterized by high yields, simple reaction conditions, fast reaction times, and high selectivity. Among many reactions tested, the 1,3-dipolar cycloaddition process has emerged as the method of choice to effect the requirements of ligating two ReviewThe modification of polymers after the successful achievement of a polymerization process represents an important task in macromolecular science. Cycloaddition reactions, among them the metal catalyzed azide/alkyne 'click' reaction (a variation of the Huisgen 1,3-dipolar cycloaddition reaction between terminal acetylenes and azides) represents an important contribution towards this endeavor. They combine high efficiency (usually above 95%) with a high tolerance of functional groups and solvents, as well as moderate reaction temperatures (25-70 8C). The present review assembles recent literature for applications of this reaction in the field of polymer science (linear polymers, dendrimers, gels) as well as the use of this and related reactions for surface modification on carbon nanotubes, fullerenes, and on solid substrates, and includes the authors own publications in this field. A number of references (>100) are included.

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Section: Click Reactions On Linear Polymers and Gelsmentioning

confidence: 55%

‘Click’ Chemistry in Polymer and Materials Science

Binder

Sachsenhofer

2007

Macromol. Rapid Commun.

1,480

866

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“…3e); a result again indicative of a robust, close packed monolayer (surface 1) that prevents the ingress of oxygenated species to the underlying silicon substrate. It is worth noting that despite the reported high reactivity of the benzylic-like 1-ferrocenylmethyl position toward nucleophilic substitution reactions, and the consequent instability of the ferrocene 2 in refluxing methanol [30], under our experimental conditions (method C) no evidence of reaction between azidomethylferrocene 2 and i-propanol was found.…”

Section: Click Reactions In Aqueous Environments Formation Of Coppermentioning

confidence: 55%

“…A detailed spectroscopic characterization of the prepared acetylenyl surface has been previously reported [10] and is not here further discussed. The solution phase copper(I)-catalyzed click variant of the Huisgen cyclo-addition reaction of azidomethylferrocene 2 with 1-alkyne species has been reported to proceed in excellent yields in refluxing organic solvents when copper(I) salts in the presence of phosphorous-type donors are used as the catalytic system [30]. We therefore started our study to assess the effect of the click conditions adopting an analogous organic solventbased protocol for our surface-based system.…”

Section: Resultsmentioning

confidence: 99%

“…Prime grade p-type (boron) silicon wafers, 100-oriented, 500 AE 25 mm thick and of 0.007 -0.009 W cm resistivity were obtained from Virginia Semiconductors, Inc. (VA, USA). Azide 2 was synthesized from ferrocenecarboxylic via the corresponding alcohol derivative hydroxymethylferrocene according to literature procedures with minor modifications [30]. Assembly of the acetylenylated Si(100) surface (surface 1) by covalent attachment of the diyne 1 followed a previously reported procedure [10].…”

Section: Methodsmentioning

confidence: 99%

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Optimization of Click Chemistry of Ferrocene Derivatives on Acetylene‐Functionalized Silicon(100) Surfaces

et al. 2008

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The optimization of the reaction conditions for copper-catalyzed azide-alkyne click cyclo-addition reactions used to covalently confine substituted ferrocene derivatives on passivated silicon(100) surfaces is reported. Variations in the observed reaction yields and the extent of surface contamination as a function of the source of the copper catalyst and the solvent system used in the click procedure were evaluated spectroscopically. The electronic communication between the ferrocene centre and the underlying semiconductor surface was investigated by means of cyclic voltammetry and found to be consistent with that expected for a well-behaved and robust redox interface.

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“…It was then purified, dried under vacuum for 48 h at 100 8C and then stored under N 2 in the glovebox. Compounds 6-Br-BMPA, [37] FcCH 2 N 3 [38] and Ph-A C H T U N G T R E N N U N G (CH 2 ) 2 N 3 [39] were prepared according to literature procedures. 11-Azidoundecane-1-thiol was synthesised following a previously described procedure.…”

Section: Methodsmentioning

confidence: 99%

A Generic Platform for the Addressable Functionalisation of Electrode Surfaces through Self‐Induced “Electroclick”

Orain

Poul

Gomila

et al. 2011

Chemistry A European J

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A novel and general strategy for the immobilisation of functional objects onto electrodes is described. The concept is based on the addition of two pendant ethynyl groups onto a bis(pyridyl)amine derivative, which acts as a molecular platform. This platform is pre-functionalised with an N(3)-tagged object of interest by Huisgen cycloaddition to one of the ethynyl groups in biphasic conditions. Hence, when complexed by Cu(II) , this molecular-object holder can be immobilised, by a "self-induced electroclick", through the second ethynyl group onto N(3)-alkanethiol self-assembled monolayers on a gold electrode. Two different functional groups, a redox innocent ((CH(2))(3)-Ph) and an electrochemical probe (ferrocene), were immobilised by following this strategy. The in situ electrochemical grafting showed, for both systems, that the kinetics of immobilisation is fast. The voltammetric characterisation of the surface-tagged functionalised copper complexes indicated that a good surface coverage was achieved and that a moderately fast electron-transfer reaction occurs. Remarkably, in the case of the redox-active ferrocenyl-immobilised system, the electrochemical response highlighted the involvement of the copper ion of the platform in the kinetics of the electron transfer to the ferrocene moiety. This platform is a promising candidate for applications in surface addressing in areas as diverse as biology and materials.

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Convenient Methods for the Synthesis of Ferrocene−Carbohydrate Conjugates

Cited by 132 publications

References 49 publications

‘Click’ Chemistry in Polymer and Materials Science

‘Click’ Chemistry in Polymer and Materials Science

Optimization of Click Chemistry of Ferrocene Derivatives on Acetylene‐Functionalized Silicon(100) Surfaces

A Generic Platform for the Addressable Functionalisation of Electrode Surfaces through Self‐Induced “Electroclick”

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