Fluorescent poly(boron enaminoketonate)s: synthesis via the direct modification of polyisoxazoles obtained from the click polymerization of a homoditopic nitrile N-oxide and diynes

Matsumura, Tohru; Koyama, Yasuhito; Uchida, Satoshi; Yonekawa, Morio; Yui, Tatsuto; Ishitani, Osamu; Takata, Toshikazu

doi:10.1038/pj.2014.31

Cited by 23 publications

(13 citation statements)

References 39 publications

(32 reference statements)

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“…Nitrile oxides participate in 1,3-dipolar cycloaddition with a range of alkynes, alkenes, and nitriles, following the reactivity order of C C > C C > C N. Takata first identified this reaction as a click system for the efficient, catalyst-free polymerization 74 of bis(nitrile oxide), and bisalkyne monomers leading to polyisoxazoles. 75,76 Nitrile oxides are highly reactive species that are often generated in situ from hydroxamoyl chloride and employed directly for sequential reactions 77,78 Takata explored kinetically stabilized aromatic nitrile oxides bearing two substituents at the ortho positions, which could be isolated. 79 Later, bulky aliphatic nitrile oxides that contain a fully substituted α-carbon were also investigated, and polymers with these moieties at the chain end have been prepared and shown to be stable.…”

Section: Nitrile Oxide-alkyne) and Alkynenitrone Cycloaddition (Anc)mentioning

confidence: 99%

“…Nitrile oxides participate in 1,3‐dipolar cycloaddition with a range of alkynes, alkenes, and nitriles, following the reactivity order of CC > CC > CN. Takata first identified this reaction as a click system for the efficient, catalyst‐free polymerization 74 of bis(nitrile oxide), and bisalkyne monomers leading to polyisoxazoles 75,76 …”

Section: Click Chemistries Employed In Polymerization and Polymer Modificationmentioning

confidence: 99%

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Click chemistry strategies for the accelerated synthesis of functional macromolecules

Geng

Shin

et al. 2021

Journal of Polymer Science

158

114

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Click chemistry is one of the most powerful strategies for constructing polymeric soft materials with precise control over architecture and functionality. In this review, we provide a comprehensive summary of the state-of-the art for synthesizing functional polymers and their expanding range of applications. The synthetic and mechanistic aspects are discussed for key reactions that fulfill "click" requirements and their applications in construction of macromolecules with linear, branched, and other complex architectures are described.

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Section: Nitrile Oxide-alkyne) and Alkynenitrone Cycloaddition (Anc)mentioning

confidence: 99%

Section: Click Chemistries Employed In Polymerization and Polymer Modificationmentioning

confidence: 99%

Click chemistry strategies for the accelerated synthesis of functional macromolecules

Geng

Shin

et al. 2021

Journal of Polymer Science

158

114

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show abstract

“…[20] This reaction has found widespread use, for example in the recently developed bioorthogonal isonitrilechlorooxime ligation, [21] or the synthesis of polyisoxazoles via click polymerisation. [22] The reactivity of nitrile-N-oxides towards many species like alkynes, alkenes and thiols makes them an attractive intermediate in reaction cascades for the formation of new species and materials alike. [23,24] We describe their application for the formation of an isoxazoline polymer gel.…”

Section: Introductionmentioning

confidence: 99%

On-Demand Release of Secondary Amine Bases for the Activation of Catalysts and Crosslinkers

Spitzbarth

Eelkema

2022

Preprint

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We demonstrate that the species present in the equilibrium of DCv ureas can be employed in reaction cascades and as triggered organocatalysts. Easily controllable stimuli like heat or addition of water shift the equilibrium towards isocyanate and free base which can function as an in situ released reagent, both catalytically and in an equimolar fashion in different reactions. While applying heat to the system leads to a reversible liberation of amine base, addition of water makes this release irreversible. We demonstrate this application of DCv ureas with two examples. Firstly, we use the liberated base to activate a protected organocatalyst for acylhydrazone formation. Secondly, this base can be employed to trigger the release of nitrile-N-oxides from chlorooximes, which can react with 4-arm PEG-acrylates to form an isoxazoline polymer gel. These findings show the utility of DCv hindered ureas beyond their application in self-healing.

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“…19 This path is commonly applied to generate nitrile-N-oxides and has found widespread use, for example in the recently developed bioorthogonal isonitrile-chlorooxime ligation, 20 or the synthesis of polyisoxazoles via click polymerisation. 21 The reactivity of nitrile-N-oxides towards many species like alkynes, alkenes and thiols makes them an attractive intermediate in reaction cascades for the formation of new species and materials alike. 22,23 We describe their application for the first formation of a thiohydroximate polymer gel.…”

Section: Introductionmentioning

confidence: 99%

On-Demand Release of Secondary Amine Bases for the Activation of Catalysts and Crosslinkers

Spitzbarth

Eelkema²

2021

Preprint

View full text Add to dashboard Cite

We demonstrate that the species present in the equilibrium of DCv ureas can be employed in reaction cascades and as triggered organocatalysts. Easily controllable stimuli like heat or addition of water shift the equilibrium towards isocyanate and free base which can function as an in situ released reagent, both catalytically and in an equimolar fashion in different reactions. While applying heat to the system leads to a reversible liberation of amine base, addition of water makes this release irreversible. We demonstrate this application of DCv ureas with two examples via <sup>1</sup>H-NMR spectroscopy. Firstly, we use the liberated base to activate a protected organocatalyst for acylhydrazone formation. Secondly, this base can be employed to trigger the release of nitrile-N-oxides from chlorooximes, which can react with 4-arm PEG-thiols to form a thiohydroximate polymer gel. These findings show the utility of DCv hindered ureas beyond their application in self-healing.

show abstract

Fluorescent poly(boron enaminoketonate)s: synthesis via the direct modification of polyisoxazoles obtained from the click polymerization of a homoditopic nitrile N-oxide and diynes

Cited by 23 publications

References 39 publications

Click chemistry strategies for the accelerated synthesis of functional macromolecules

Click chemistry strategies for the accelerated synthesis of functional macromolecules

On-Demand Release of Secondary Amine Bases for the Activation of Catalysts and Crosslinkers

On-Demand Release of Secondary Amine Bases for the Activation of Catalysts and Crosslinkers

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