Catalyst- and Solvent-Free Click Synthesis of Cyclodextrin-Based Polyrotaxanes Exploiting a Nitrile <i>N</i>-Oxide

Jang, Keumhee; Miura, Kaori; Koyama, Yasuhito; Takata, Toshikazu

doi:10.1021/ol3011024

Cited by 52 publications

(19 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Takata et al demonstrated that no catalyst was required to synthesize [ n ]rotaxanes under solvent‐free conditions when using dipolar cycloaddition between nitrile N ‐oxides and alkenes to interlock PEG‐ and PTHF‐based polyrotaxanes (Scheme ) . The threading of the allyl‐terminated linear guests through the cavities of α‐CD or PMα‐CD was achieved in solution through three sequential steps: (a) sonication (room temperature, 30 min), (b) standing overnight at room temperature, and (c) collecting the solid precipitate through centrifugation.…”

Section: Stoppering Through 13‐dipolar Cycloadditionsmentioning

confidence: 99%

Solvent‐free synthesis of rotaxanes

Inthasot

Tai

Chiu

2019

J Chinese Chemical Soc

View full text Add to dashboard Cite

Rotaxane‐type (macro)molecules are important materials in various fields of research, with many approaches for their synthesis having been developed over the past 30 years or so. When prepared in solution, the efficiency of interlocking pseudorotaxane complexes into the corresponding rotaxanes relies, to a great extent, on the affinity between the host and guest components; these interactions are not always sufficiently strong to overcome the deleterious effects of high reaction temperatures, competitive solvents, and low concentrations. Upon evaporating the solvent, however, the concentrations of the host and guest species increase significantly and, ultimately, their corresponding pseudorotaxanes can be generated with high efficiency in the solvent‐free residue. Furthermore, in the absence of the solvent, the influence of any disrupting byproducts (generated during the interlocking process) on the complexation equilibrium can also be largely reduced. Therefore, high synthetic efficiency and low consumption of solvents and energy can be expected when synthesizing rotaxanes under solvent‐free conditions. This mini‐review covers the main publications dealing with the solvent‐free syntheses of rotaxanes – those in which the interlocking step involves no solvent (or only a trace of it).

show abstract

Section: Stoppering Through 13‐dipolar Cycloadditionsmentioning

confidence: 99%

Solvent‐free synthesis of rotaxanes

Inthasot

Tai

Chiu

2019

J Chinese Chemical Soc

View full text Add to dashboard Cite

show abstract

“…Building upon our previous study, [24][25][26][27][28][29][30][31][32][33][34][35][36] we selected bis(2-alcoxy-naphthalene nitrile N-oxide) as a skeleton, speculating that it should serve well as a framework for a sufficiently-stabilized homoditopic nitrile N-oxide. Synthesis of the homoditopic nitrile N-oxide 1 was accomplished in 58% overall yield via a three-step reaction (Scheme 1, m.p.…”

Section: Synthesis Of Bis(nitrile N-oxide) 1 and Poly(boron Enaminokementioning

confidence: 99%

“…applications not only to polymeric materials but also supramolecular chemistry because we have previously reported effective synthesis of rotaxane and polyrotaxane exploiting a cycloaddition of stable nitrile N-oxide. 16,27,30,33,36 The study of stimuli-responsive fluorescent switching system using BEK-containing supramolecular skeleton will be important for future. …”

Section: Synthesis Of Bis(nitrile N-oxide) 1 and Poly(boron Enaminokementioning

confidence: 99%

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

Koyama

Uchida

et al. 2014

Polym J

Self Cite

View full text Add to dashboard Cite

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Catalyst- and Solvent-Free Click Synthesis of Cyclodextrin-Based Polyrotaxanes Exploiting a Nitrile N-Oxide

Cited by 52 publications

References 54 publications

Solvent‐free synthesis of rotaxanes

Solvent‐free synthesis of rotaxanes

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

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

Contact Info

Product

Resources

About