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A rational entry to cyclic polymers via spontaneous and selective cyclization reactions

Polymer Journal volume 53, pages 257–269 (2021)Cite this article

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Abstract

This focus review describes the status quo of synthetic routes to cyclic compounds and cyclic polymers via spontaneous cyclization processes using (1) rotaxane chemistry and (2) dynamic covalent chemistry. Systems with rotaxane-based structures undergo spontaneous and selective cyclization of two self-complementary molecules and a macromolecular rotaxane switch, where the relative position of each component can be controlled, which results in a topology change from linear to cyclic. Systems based on dynamic covalent chemistry use exchange reactions of bis(2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS) units that behave as stable linkages at r.t. and exchange disulfide bonds upon heating. Controlling the dynamic nature of BiTEMPS-based low-molecular-weight compounds and polymers thus provides cyclic topologies via spontaneous and selective cyclization processes.

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Acknowledgements

The author would like to express his gratitude to all his past and present colleagues for their valuable contributions to this focus review. The author is deeply indebted to Prof. Toshikazu Takata (Hiroshima University) and Prof. Hideyuki Otsuka (Tokyo Institute of Technology) for their continuous encouragement and constructive discussions. This research was supported by KAKENHI grants 16K17910, 18K14272, and 20H02783 from the Japan Society for the Promotion of Science (JSPS), the Mizuho Foundation for the Promotion of Science, the Eno Scientific Foundation, the Iketani Science and Technology Foundation, and JST PRESTO grant JPMJPR18L1 (Japan).

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    Daisuke Aoki

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Aoki, D. A rational entry to cyclic polymers via spontaneous and selective cyclization reactions. Polym J 53, 257–269 (2021). https://doi.org/10.1038/s41428-020-00422-6

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