Efficient synthesis of pure monotosylated beta-cyclodextrin and its dimers

Tripodo, Giuseppe; Wischke, Christian; Neffe, Axel T.; Lendlein, Andreas

doi:10.1016/j.carres.2013.08.018

Cited by 62 publications

(45 citation statements)

References 27 publications

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“…For this purpose, the selective monotosylation of the free CD was chosen. Several methods for 6-O-tosylation have already been published [23–26]. Unfortunately, most of them lead to mixtures of mono- and multi-tosylated products, which cannot be separated by precipitation from acetone or crystalization from water.…”

Section: Resultsmentioning

confidence: 99%

A complete series of 6-deoxy-monosubstituted tetraalkylammonium derivatives of α-, β-, and γ-cyclodextrin with 1, 2, and 3 permanent positive charges

Popr¹,

Hybelbauerová²,

Jindřich³

2014

Beilstein J. Org. Chem.

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SummaryAn efficient synthetic route toward the preparation of a complete series of monosubstituted tetraalkylammonium cyclodextrin (CD) derivatives is presented. Monotosylation of native CDs (α-, β-, γ-) at position 6 gave the starting material. Reaction of monotosylate (mono-Ts-CD) with 45% aqueous trimethylamine gave CDs substituted with one cationic functional group in a single step. Derivatives equipped with a substituent containing two cationic sites separated by an ethylene or a propylene linker were prepared by reacting mono-Ts-CD with neat N,N,N’-trimethylethane-1,2-diamine or N,N,N’-trimethylpropane-1,3-diamine and subsequent methylation by CH3I in good yields. Finally, analogues bearing a moiety with three tetraalkylammonium sites were synthesized by reacting mono-Ts-CD with bis(3-aminopropyl)amine and subsequent methylation. The majority of the presented reactions are very straightforward with a simple work-up, which avoids the need of chromatographic separation. Thus, these reactions are suitable for the multigram-scale production of monosubstituted cationic CDs.

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Section: Resultsmentioning

confidence: 99%

A complete series of 6-deoxy-monosubstituted tetraalkylammonium derivatives of α-, β-, and γ-cyclodextrin with 1, 2, and 3 permanent positive charges

Popr¹,

Hybelbauerová²,

Jindřich³

2014

Beilstein J. Org. Chem.

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“…Optimizing the monotosylation of CDs has been the subjecto fm any studies. [14,[31][32][33]], However,s electivity remains ac hallengea nd difficult chromatographic separations, and crystallizations, are required to remove side products.T his monoderivatization methodology enables the introduction of av ariety of substituents, such as am onoazide, amine, hydroxylamine, or thiol, which can then be further modified. [15,34,35] Amine-functionalized b-CD is ap articularly desirable scaffold, whichh as been conjugated to av ariety of biologicallyr elevant molecules includingg lycodendrimers, [36,37] peptides, [38] proteins, [39] and drugs [2] .…”

Section: Introductionmentioning

confidence: 99%

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Vurgun

Gómez‐Biagi

Nitz

2015

Chemistry A European J

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Herein, we report the selective mono-derivatization of heptakis[6-deoxy-6-(2-aminoethylsulfanyl)]-β-CD (1) through a guest-mediated covalent capture strategy. The use of guests functionalized with cleavable linkers enables the installation of an amine-orthogonal thiol group on the primary rim of 1 as a handle for further transformations to the β-CD scaffold. Applying this methodology, two novel monoderivatized β-CDs were obtained in good yield and high purity. Both of these monoacylated CDs were amenable to facile linker cleavage and further modification at the resulting thiol group. This methodology can be applied towards the synthesis heterofunctionalized β-CD constructs for analyte sensing, drug delivery, and other applications.

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“…At the introduction of 2 to 5 bromine atoms difficultly separable position isomers can form. 2 From the numerous methods of monotosylate 3 preparation [15] we chose the procedure from [14] as the most reliable and efficient.…”

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confidence: 99%

Synthesis of monocationic β-cyclodextrin derivatives

et al. 2017

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Reactions of 6-bromo-and 6-iodo-6-deoxy-β-cyclodextrin with organic amines of diverse nature afforded a series of monocationic derivatives with aminium groups located in the cyclodextrin scaffold on the side of the primary hydroxy groups. The structure and composition of the obtained cationic β-cyclodextrin derivatives were confirmed by 1 H and 13 C NMR data.Cationic cyclodextrin derivatives owing to the positive charge on the cyclodextrin matrix are capable of incorporation in biologic membranes and of penetration through biologic barriers [1-4]. They are potential objects of pharmacological studies as drug carriers and also as carriers for the DNA delivery (vectorization) in the gene therapy [3][4][5][6][7].The preparation of cationic derivatives commonly utilizes 6-azido-6-deoxy cyclodextrin derivatives that are converted into amines by treating with triphenylphosphine in aqueous ammonia [8,9]. However this method possesses a limitation since it is suitable only for the preparation of aminium cyclodextrin derivatives from primary amines.

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Efficient synthesis of pure monotosylated beta-cyclodextrin and its dimers

Cited by 62 publications

References 27 publications

A complete series of 6-deoxy-monosubstituted tetraalkylammonium derivatives of α-, β-, and γ-cyclodextrin with 1, 2, and 3 permanent positive charges

A complete series of 6-deoxy-monosubstituted tetraalkylammonium derivatives of α-, β-, and γ-cyclodextrin with 1, 2, and 3 permanent positive charges

Access to Versatile β‐Cyclodextrin Scaffolds through Guest‐Mediated Monoacylation

Synthesis of monocationic β-cyclodextrin derivatives

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