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Organo–metal cooperative catalysis for C(sp3)–H alkylation polymerization

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Abstract

The reversible deactivation process is the essence of a variety of modern polymerization technologies, which have found wide applications in both academia and industry. However, this process seldom employs hydrogen atoms as the chain-end groups due to the lack of effective control in carbon–hydrogen functionalization polymerization (CHFP). Cooperative catalysis, especially the interplay between an organocatalyst and a metal complex, may offer a solution to the lack of control in CHFP. Here, we report a proof of concept in ring-opening polymerization of cyclopropanes using commercially available MgBr2 and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) for a C(sp3)–H initiator system. This approach imparts cooperative activation towards chain-end hydrogen atoms and monomers, as well as reversible chain-end deprotonation and protonation to enable C(sp3)–H alkylation polymerization. This polymerization allows multiple-site chain growth and exhibits temperature dependence, thus providing unprecedented access to sequence-controlled copolymers.

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Fig. 1: C–H functionalization polymerization.
Fig. 2: Scope of initiators and cyclopropane monomers.
Fig. 3: Kinetics and the probe of polymer chain-end groups.
Fig. 4: Mechanistic study.
Fig. 5: DFT calculations.
Fig. 6: Proposed polymerization mechanism.
Fig. 7: Poly(cyclopropanes) with advanced microstructures.

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Data availability

The data supporting the findings of this study are available within the Article and its Supplementary Information.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (no. 22101273 to D.-F.C. and 21831007 to L.-Z.G.), the Anhui Provincial Natural Science Foundation (no. 2108085MB30 to D.-F.C.) and startup funding from the University of Science and Technology of China (D.-F.C.).

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Authors and Affiliations

  1. Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Yang-Yang Li, Shao-Qiu Zheng, Dian-Feng Chen & Liu-Zhu Gong

  2. Department of Chemistry, University of Science and Technology of China, Hefei, China

    Teng Xie, Ling Zhu & Liu-Zhu Gong

  3. Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, China

    Dian-Feng Chen

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  1. Yang-Yang Li
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Contributions

D.-F.C. and L.-Z.G. conceived the idea of the project. Y.-Y.L. and T.X. synthesized the monomers. Y.-Y.L. performed the polymerizations and data analysis. L.Z. and S.-Q.Z. performed the DFT calculations. D.-F.C. and L.-Z.G. directed the investigations and co-wrote the manuscript.

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Correspondence to Dian-Feng Chen or Liu-Zhu Gong.

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Nature Synthesis thanks Yves Gnanou and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Experimental Details, Figs. 1–74 and Tables 1–13.

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Li, YY., Xie, T., Zhu, L. et al. Organo–metal cooperative catalysis for C(sp3)–H alkylation polymerization. Nat. Synth 2, 1232–1242 (2023). https://doi.org/10.1038/s44160-023-00389-1

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