Preparation of a Reversible Redox‐Controlled Cage‐Type Molecule Linked by Disulfide Bonds

Horng, Yih-Chern; Lin, Tzung Lung; Tu, Cheng Yi; Sung, Ting Ju; Hsieh, Chang Chih; Hu, Ching‐Han; Lee, Hon Man; Kuo, Ting Shen

doi:10.1002/ejoc.200900044

Cited by 30 publications

(15 citation statements)

References 29 publications

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“…[1] The assembly of purely organic cages can be achieved using dynamic covalent chemistry. [2][3][4][5][6] Along these lines, imine condensations have been most widely used to date, [3] but the syntheses of cages based on boronic ester condensations, [4] thiol-disulfide exchange reactions, [5] or olefin metathesis [6] have also been described. Metallasupramolecular chemistry has been successfully merged with dynamic covalent chemistry by performing imine condensations in the first coordination sphere of metal ions.…”

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confidence: 99%

Combining Metallasupramolecular Chemistry with Dynamic Covalent Chemistry: Synthesis of Large Molecular Cages

et al. 2010

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Molecular cages with large internal voids are best synthesized by assembly of multiple building blocks under thermodynamic control. To connect the building blocks, metal-ligand interactions are commonly employed. [1] The resulting coordination cages have found numerous applications. For example, they can be used as nanoreactors for chemical transformations, as delivery agents for anticancer compounds, or for the stabilization of highly reactive guest molecules. [1] The assembly of purely organic cages can be achieved using dynamic covalent chemistry. [2][3][4][5][6] Along these lines, imine condensations have been most widely used to date, [3] but the syntheses of cages based on boronic ester condensations, [4] thiol-disulfide exchange reactions, [5] or olefin metathesis [6] have also been described. Metallasupramolecular chemistry has been successfully merged with dynamic covalent chemistry by performing imine condensations in the first coordination sphere of metal ions. [7] This approach has proven extremely robust due to the resulting mutual stabilization of both the metal complex and the imine bond. [8] Fascinating recent results include the stabilization of molecular P 4 within a coordination cage, [9] and the synthesis of a Borromean ring and a Solomon knot. [10] Our group is interested in synthesizing complex molecular architectures by combining metallasupramolecular chemistry with dynamic covalent chemistry in an orthogonal fashion. Recently, we described a first success in this direction: a 52membered macrocycle was obtained by the concomitant formation of reversible imine, boronate ester, and rheniumnitrogen bonds. [11,12] Herein, we describe how the polycondensation of triamines with metallamacrocyclic building blocks, containing pendent aldehyde groups, has enabled the facile synthesis of several new nanoscopic cages.The reaction of a triamine with a trialdehyde can result in the formation of a [4+4] condensation product, provided that the reactants have complementary shape and rigidity. We hypothesized that it should be possible to make expanded structures by replacing either the triamine or the trialdehyde with trinuclear metallamacrocycles having appropriate amine or aldehyde functionalities in their ligand peripheries. To implement such a reaction, we synthesized the formylsubstituted 3-hydroxy-2-pyridone ligand 1 (Scheme 1) using standard organic transformations (Supporting Information). Subsequent reaction with [{(arene)RuCl 2 } 2 ] complexes in the presence of base gave the trinuclear macrocycles 2 a (arene = p-cymene) and 2 b (arene = 1,3,5-Me 3 C 6 H 3 ; Scheme 1). The spectroscopic features of 2 a and 2 b were similar to what has been reported for other organometallic trimers with bridging 3-hydroxy-2-pyridone ligands; [13] moreover, crystallographic analysis of 2 b confirmed that a trinuclear complex had formed (Supporting Information, Figure S1). [14] The three aldehyde groups are 7.8 apart (average O···O distance) and oriented towards the same face of the macrocyclic framework. Scheme 1...

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confidence: 99%

Combining Metallasupramolecular Chemistry with Dynamic Covalent Chemistry: Synthesis of Large Molecular Cages

et al. 2010

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“…[110][111][112][113][114] Da die C-C-Bindungsknüpfung in diesem Fall nur in Gegenwart eines Katalysators reversibel ist, sind solche Ansätze besonders fürd ie Synthese von stabilen Käfigen interessant. [118] Die Bildung von Disulfiden wurde nur in einigen wenigen Fällen fürd ie Bildung von Käfigen eingesetzt, [119][120][121] und fürC OFs sind bis jetzt noch überhaupt keine Beispiele bekannt, obwohl diese Reaktion fürd ynamisch-kovalente Bibliotheken gut etabliert ist. Die Polykondensation von Quadratsäure mit einem Te traaminoporphyrin führte zur Bildung eines kristallinen Squarainnetzwerks.…”

Section: Dynamisch-kovalente Reaktionenunclassified

“…[117] Wuest und Mitarbeiter nutzten die reversible Dimerisierung von Nitrosogruppen unter Bildung von Azodioxiden fürdie Synthese von einkristallinen 3D-COFs. [118] Die Bildung von Disulfiden wurde nur in einigen wenigen Fällen fürd ie Bildung von Käfigen eingesetzt, [119][120][121] [122] und Hybridkäfige konnten über mehrfache Ugi-Vierkomponentenreaktionen erhalten werden. [123]…”

Section: Dynamisch-kovalente Reaktionenunclassified

Kovalente organische Netzwerke und Käfigverbindungen: Design und Anwendungen von polymeren und diskreten organischen Gerüsten

Beuerle

Gole

2018

Angewandte Chemie

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Poröse organische Materialien sind eine aufstrebende Klasse funktionaler Nanostrukturen mit beispiellosen Eigenschaften. Die dynamisch‐kovalente Organisation kleiner organischer Bausteine unter thermodynamischer Kontrolle wird dabei für die verblüffend einfache Bildung komplexer Architekturen in Eintopfreaktionen genutzt. In diesem Aufsatz werden die grundlegenden Designprinzipien analysiert, die zur Bildung von entweder kovalenten organischen Netzwerken als kristalline poröse Polymere oder kovalenten organischen Käfigverbindungen als formgetreue molekulare Objekte führen. Konventionelle Synthesevorschriften und Analysemethoden werden neben ausgefeilteren Strategien, wie postsynthetische Modifizierungen oder Selbstsortierung, diskutiert. Gegebenenfalls werden die entsprechenden Eigenschaften und Besonderheiten von polymeren Netzwerken und diskreten organischen Käfigen verglichen. Darüber hinaus wird das Potenzial dieser Materialien für Anwendungen, von der Gasspeicherung über die Katalyse bis hin zur organischen Elektronik, erörtert.

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“…Another promising alternative approach to synthesize POCs is based on dynamic covalent chemistry (DCC) by reversible bond formation. The most widely practiced DCC approach in the self-assembly of porosity molecular cages include imine reactions [87,88], boronic acid condensation [89], disulfide exchange [90], alkene/alkyne metathesis [91], etc. During the last few years, a large number of novel POCs could be obtained from simple precursors in reasonable yield by the DCC approach.…”

Section: Chiral Porous Organic Cages As Chiral Stationary Phases For Gcmentioning

confidence: 99%

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography

Xie

Yuan

2016

J of Separation Science

108

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Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced.

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Preparation of a Reversible Redox‐Controlled Cage‐Type Molecule Linked by Disulfide Bonds

Cited by 30 publications

References 29 publications

Combining Metallasupramolecular Chemistry with Dynamic Covalent Chemistry: Synthesis of Large Molecular Cages

Combining Metallasupramolecular Chemistry with Dynamic Covalent Chemistry: Synthesis of Large Molecular Cages

Kovalente organische Netzwerke und Käfigverbindungen: Design und Anwendungen von polymeren und diskreten organischen Gerüsten

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography

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