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Telechelic sequence-defined oligoamides : their step-economical synthesis, depolymerization and use in polymer networks

Irene De Franceschi (UGent) , Nezha Badi (UGent) and Filip Du Prez (UGent)
(2024) CHEMICAL SCIENCE. 15(8). p.2805-2816
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Abstract
The application of sequence-defined macromolecules in material science remains largely unexplored due to their challenging, low yielding and time-consuming synthesis. This work first describes a step-economical method for synthesizing unnatural sequence-defined oligoamides through fluorenylmethyloxycarbonyl chemistry. The use of a monodisperse soluble support enables homogeneous reactions at elevated temperature (up to 65 C-degrees), leading to rapid coupling times (<10 min) and improved synthesis protocols. Moreover, a one-pot procedure for the two involved iterative steps is demonstrated via an intermediate quenching step, eliminating the need for in-between purification. The protocol is optimized using gamma-aminobutyric acid (GABA) as initial amino acid, and the unique ability of the resulting oligomers to depolymerize, with the formation of cyclic gamma-butyrolactame, is evidenced. Furthermore, in order to demonstrate the versatility of the present protocol, a library of 17 unnatural amino acid monomers is synthesized, starting from the readily available GABA-derivative 4-amino-2-hydroxybutanoic acid, and then used to create multifunctional tetramers. Notably, the obtained tetramers show higher thermal stability than a similar thiolactone-based sequence-defined macromolecule, which enables its exploration within a material context. To that end, a bidirectional growth approach is proposed as a greener alternative that reduces the number of synthetic steps to obtain telechelic sequence-defined oligoamides. The latter are finally used as macromers for the preparation of polymer networks. We expect this strategy to pave the way for the further exploration of sequence-defined macromolecules in material science.
Keywords
SOLID-PHASE SYNTHESIS, BETA-PEPTIDES, POLYAMIDE 6, OLIGOMERS, COPOLYMERS, STRATEGY, CHAIN, END

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MLA
De Franceschi, Irene, et al. “Telechelic Sequence-Defined Oligoamides : Their Step-Economical Synthesis, Depolymerization and Use in Polymer Networks.” CHEMICAL SCIENCE, vol. 15, no. 8, 2024, pp. 2805–16, doi:10.1039/d3sc04820a.
APA
De Franceschi, I., Badi, N., & Du Prez, F. (2024). Telechelic sequence-defined oligoamides : their step-economical synthesis, depolymerization and use in polymer networks. CHEMICAL SCIENCE, 15(8), 2805–2816. https://doi.org/10.1039/d3sc04820a
Chicago author-date
De Franceschi, Irene, Nezha Badi, and Filip Du Prez. 2024. “Telechelic Sequence-Defined Oligoamides : Their Step-Economical Synthesis, Depolymerization and Use in Polymer Networks.” CHEMICAL SCIENCE 15 (8): 2805–16. https://doi.org/10.1039/d3sc04820a.
Chicago author-date (all authors)
De Franceschi, Irene, Nezha Badi, and Filip Du Prez. 2024. “Telechelic Sequence-Defined Oligoamides : Their Step-Economical Synthesis, Depolymerization and Use in Polymer Networks.” CHEMICAL SCIENCE 15 (8): 2805–2816. doi:10.1039/d3sc04820a.
Vancouver
1.
De Franceschi I, Badi N, Du Prez F. Telechelic sequence-defined oligoamides : their step-economical synthesis, depolymerization and use in polymer networks. CHEMICAL SCIENCE. 2024;15(8):2805–16.
IEEE
[1]
I. De Franceschi, N. Badi, and F. Du Prez, “Telechelic sequence-defined oligoamides : their step-economical synthesis, depolymerization and use in polymer networks,” CHEMICAL SCIENCE, vol. 15, no. 8, pp. 2805–2816, 2024.
@article{01HRRXV43YN02NWJ0JY4QT3NJ4,
  abstract     = {{The application of sequence-defined macromolecules in material science remains largely unexplored due to their challenging, low yielding and time-consuming synthesis. This work first describes a step-economical method for synthesizing unnatural sequence-defined oligoamides through fluorenylmethyloxycarbonyl chemistry. The use of a monodisperse soluble support enables homogeneous reactions at elevated temperature (up to 65 C-degrees), leading to rapid coupling times (<10 min) and improved synthesis protocols. Moreover, a one-pot procedure for the two involved iterative steps is demonstrated via an intermediate quenching step, eliminating the need for in-between purification. The protocol is optimized using gamma-aminobutyric acid (GABA) as initial amino acid, and the unique ability of the resulting oligomers to depolymerize, with the formation of cyclic gamma-butyrolactame, is evidenced. Furthermore, in order to demonstrate the versatility of the present protocol, a library of 17 unnatural amino acid monomers is synthesized, starting from the readily available GABA-derivative 4-amino-2-hydroxybutanoic acid, and then used to create multifunctional tetramers. Notably, the obtained tetramers show higher thermal stability than a similar thiolactone-based sequence-defined macromolecule, which enables its exploration within a material context. To that end, a bidirectional growth approach is proposed as a greener alternative that reduces the number of synthetic steps to obtain telechelic sequence-defined oligoamides. The latter are finally used as macromers for the preparation of polymer networks. We expect this strategy to pave the way for the further exploration of sequence-defined macromolecules in material science.}},
  author       = {{De Franceschi, Irene and Badi, Nezha and Du Prez, Filip}},
  issn         = {{2041-6520}},
  journal      = {{CHEMICAL SCIENCE}},
  keywords     = {{SOLID-PHASE SYNTHESIS,BETA-PEPTIDES,POLYAMIDE 6,OLIGOMERS,COPOLYMERS,STRATEGY,CHAIN,END}},
  language     = {{eng}},
  number       = {{8}},
  pages        = {{2805--2816}},
  title        = {{Telechelic sequence-defined oligoamides : their step-economical synthesis, depolymerization and use in polymer networks}},
  url          = {{http://doi.org/10.1039/d3sc04820a}},
  volume       = {{15}},
  year         = {{2024}},
}

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