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Sequence-defined oligo/poly(ester-amide-ester)s via an orthogonal nucleophilic substitution reaction and a Passerini reaction

Polymer Journal volume 52, pages 133–143 (2020)Cite this article

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Abstract

We report the facile synthesis of sequence-defined, uniform oligo(ester-amide-ester)s, and periodic poly(ester-amide-ester)s composed of ɑ-hydroxy acids and ɑ-amino acids. The synthetic strategy for preparing the oligomers involves two sequential steps with bromoacetic acid and potassium isocyanoacetate as the key building blocks. (1) The first step is a nucleophilic substitution reaction between a bromoacetic ester and potassium isocyanoacetate to generate a new isocyanoacetic ester, (2) and the second is a Passerini reaction of the formed isocyanoacetic ester with an aldehyde and bromoacetic acid to form a longer bromoacetic ester with an ester-amide linkage and a side-group originating from the aldehyde. Repeating this cycle affords sequence-defined uniform oligo(ester-amide-ester)s with different side groups. This strategy efficiently provides uniform, symmetrical oligo(ester-amide-ester)s via an iterative approach. Furthermore, two strategies were examined to obtain sequence-defined periodic poly(ester-amide-ester)s through the polycondensation of different oligomers. The polycondensation based on the nucleophilic substitution of α,ω-bromo carboxylic acids as the oligomer was less effective, while the DIC/DPTS-mediated polycondensation of α,ω-hydroxy carboxylic acids as the sequence-defined oligomer was efficient enough to afford high-molecular-weight periodic poly(ester-amide-ester)s.

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Acknowledgements

This work was supported in part by the National Natural Science Foundation of China (Nos 21534001 and 21871014).

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  1. Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Department of Polymer Science and Engineering, College of Chemistry and Molecular Engineering, Center for Soft Matter Science and Engineering, Peking University, 100871, Beijing, China

    Yao-Zong Wang, Jia-Chen Wang, Yu-Huan Wu, Chang-Xia Shi, Fu-Sheng Du & Zi-Chen Li

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Correspondence to Fu-Sheng Du or Zi-Chen Li.

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Wang, YZ., Wang, JC., Wu, YH. et al. Sequence-defined oligo/poly(ester-amide-ester)s via an orthogonal nucleophilic substitution reaction and a Passerini reaction. Polym J 52, 133–143 (2020). https://doi.org/10.1038/s41428-019-0272-6

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