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Dynamic self-correcting nucleophilic aromatic substitution

Nature Chemistry volume 10, pages 1023–1030 (2018)Cite this article

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Abstract

Dynamic covalent chemistry, with its ability to correct synthetic dead-ends, allows for the synthesis of elaborate extended network materials in high yields. However, the limited number of reactions amenable to dynamic covalent chemistry necessarily confines the scope and functionality of materials synthesized. Here, we explore the dynamic and self-correcting nature of nucleophilic aromatic substitution (SNAr), using ortho-aryldithiols and ortho-aryldifluorides that condense to produce redox-active thianthrene units. We demonstrate the facile construction of two-, three- and four-point junctions by reaction between a dithiol nucleophile and three different model electrophiles that produces molecules with two, three and four thianthrene moieties, respectively, in excellent yields. The regioselectivity observed is driven by thermodynamics; other connections form under kinetic control. We also show that the same chemistry can be extended to the synthesis of novel ladder macrocycles and porous polymer networks with Brunauer–Emmett–Teller surface area of up to 813 m2 g−1.

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Fig. 1: Reactions between a dithiol or tetrathiol nucleophile and three different model electrophiles.
Fig. 2: Dynamic, self-correcting SNAr reaction.
Fig. 3: Facile exchange of dithiol nucleophiles.
Fig. 4: Synthesis of ladder macrocycle 15.
Fig. 5: Model reaction, synthesis and characterization of porous ladder polymer network 19.
Fig. 6: Model reaction, synthesis and characterization of porous ladder polymer network 20.

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Acknowledgements

This work was supported by an Abdul Latif Jameel World Water and Food Security Lab (J-WAFS) Seed Grant. W.J.O. is indebted to the Agency for Science, Technology and Research (A*STAR), Singapore, for a graduate scholarship. The authors thank M. He for discussions and XPS measurements, B. Yoon for SEM measurements, R. Cook and A. Leshinsky for MALDI measurements, R. G. Griffin and D. Banks for ssNMR measurements, and I. Jeon for X-ray diffraction measurements.

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  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Wen Jie Ong & Timothy M. Swager

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  1. Wen Jie Ong
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W.J.O. performed all of the experiments. Both authors designed the experiments, analysed the data, and wrote the manuscript.

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Correspondence to Timothy M. Swager.

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Supplementary Information

Supplementary Figures 1–22; Cyclic voltammetry; Characterization of compounds 19 and 20; Experimental Procedures; NMR spectra

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Ong, W.J., Swager, T.M. Dynamic self-correcting nucleophilic aromatic substitution. Nature Chem 10, 1023–1030 (2018). https://doi.org/10.1038/s41557-018-0122-8

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