Synthesis of a Kinetically Stabilized Homoditopic Nitrile <i>N</i>-Oxide Directed toward Catalyst-free Click Polymerization

Lee, Young-Gi; Yonekawa, Morio; Koyama, Yasuhito; Takata, Toshikazu

doi:10.1246/cl.2010.420

Cited by 39 publications

(25 citation statements)

References 22 publications

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“…[3][4][5] From the viewpoint of polymer synthesis, to say nothing of the polyaddition via click chemistry, [6][7][8][9][10][11] polymers possessing clickable pendant groups 12,13 and/or end-functionalities [14][15][16] have attracted researchers' attention, as such polymers can be used as 'building blocks' for syntheses of highly functionalized polymers, 17,18 construction of sophisticated topology, 19,20 and surface modification 21,22 .…”

Section: Introductionmentioning

confidence: 99%

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

2015

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Isotactic and syndiotactic poly(methyl methacrylate)s with orthogonally double-clickable terminal ends, that is, α,β-unsaturated ester for Michael addition-type thiol-ene reaction and azide or alkynyl groups for azide-alkyne click reaction, were prepared via terminating reaction of stereospecific anionic polymerization with propargyl and 2-chloroethyl α-(chloromethyl)acrylates. The subsequent polymer modification via double click reaction proceeded quantitatively in one -pot system under ambient conditions. The facile and almost quantitative double-end-functionalization would open a new material design based on stereoregular PMMAs with controlled molecular weights.

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Section: Introductionmentioning

confidence: 99%

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

2015

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“…46 The reaction of diethynyl-functionalized DB24C8 11 with 12 in refluxing CHCl 3 without any catalyst afforded the isoxazole-containing poly(crown ether) (polyisoxazole-13) in quantitative yield by poly[2+3]cycloaddition. The molecular weight and its distribution, estimated by SEC based on polystyrene standards, were M w ¼33 700 and M w /M n ¼1.7.…”

Section: Synthesis Of Poly(crown Ether)smentioning

confidence: 99%

Polymer architectures assisted by dynamic covalent bonds: synthesis and properties of boronate-functionalized polyrotaxane and graft polyrotaxane

Koyama

Suzuki

Asakawa

et al. 2011

Polym J

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Poly [2]rotaxane and graft polyrotaxane were synthesized from a mixture of poly(crown ether) (polyester-10 and polyisoxazole-13) as a trunk polymer, boronic-acid-terminated secondary ammonium salt 5 as an axle component, and diol as an end-capping group by pseudorotaxane formation and subsequent catalyst-free dehydrative bondage between the boronic acid and the diol moieties. Trunk polymers 10 and 13 were prepared by copolymerization of diol-or diyne-substituted dibenzo-24-crown-8-ether 9 or 11 and ditopic comonomers such as bifunctional acid dichloride and nitrile N-oxide. The use of the sufficiently bulky and stable homoditopic nitrile N-oxide 12 gave the high-molecular-weight isoxazole-containing poly(crown ether) 13 efficiently and without accidental penetration of the propagation end into the crown cavity, which would have caused gelation. The treatment of these poly(crown ether)s with boronic acid 5 in CH 2 Cl 2 gave the corresponding polypseudorotaxanes, and subsequent graftonto reaction with pinacol and a polymeric terminal diol gave poly[2]rotaxane and graft polyrotaxane. The chemical stability of these supramolecular architectures primarily depends on the bulkiness of the diol group as the end-capping moiety and the inherence originating from the dynamic covalent bond of boronate, as determined by detailed 1 H nuclear magnetic resonance study of model [2]rotaxanes 6-8 and the dissociation behavior of the polymers.

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“…This agent enables the easy molecular integration of various nucleophiles onto C=C-, C≡C-, and C≡N-containing polymers in the presence of an appropriate catalyst. Building on our previous reports [23][24][25][26][27][28][29][30][31][32], in this study, we describe a convenient protocol to introduce a masked ketene moiety to 4 unsaturated-bond-containing common polymers via a catalyst-free click reaction.…”

Section: Introductionmentioning

confidence: 99%

Catalyst-free click cascade functionalization of unsaturated-bond-containing polymers using masked-ketene-tethering nitrile N-oxide

Cheawchan

Koyama

Uchida

et al. 2013

Polymer

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We developed a facile protocol for grafting-onto and cross-linking unsaturated-bond-containing common polymers via the formation of masked-ketene-functionalized polymers. The protocol utilizes a cascade functionalization agent 1 that has nitrile N-oxide and masked ketene functionalities. Through the model ligation reactions using 1, it turned out that the 1 facilitates the catalyst-free click introduction of masked ketene moieties to the unsaturated bonds such as C≡N and C=C bonds, capable of undergoing catalyst-free ligation with not only a nucleophilic amine but also a neutral alcohol with low nucleophilicity. On the basis of these results, the catalyst-free grafting reactions of PEG onto EPDM and PAN using 1 were performed to afford the corresponding graft copolymers in excellent conversion yields. In addition, it was also revealed that heating of both PAN and NR with masked ketene moieties at 250 °C for 1 h without catalyst enables the efficient conversion to give the respective cross-linked polymers.

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Synthesis of a Kinetically Stabilized Homoditopic Nitrile N-Oxide Directed toward Catalyst-free Click Polymerization

Cited by 39 publications

References 22 publications

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

Stereoregular poly(methyl methacrylate) with double-clickable ω-end: synthesis and click reaction

Polymer architectures assisted by dynamic covalent bonds: synthesis and properties of boronate-functionalized polyrotaxane and graft polyrotaxane

Catalyst-free click cascade functionalization of unsaturated-bond-containing polymers using masked-ketene-tethering nitrile N-oxide

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