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Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates

Nature Chemistry volume 9, pages 10831088 (2017) | Download Citation

Abstract

Polysulfates and polysulfonates possess exceptional mechanical properties making them potentially valuable engineering polymers. However, they have been little explored due to a lack of reliable synthetic access. Here we report bifluoride salts (Q+[FHF], where Q+ represents a wide range of cations) as powerful catalysts for the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl silyl ethers and aryl fluorosulfates (or alkyl sulfonyl fluorides). The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading (down to 0.05 mol%). Using this chemistry, we are able to prepare polysulfates and polysulfonates with high molecular weight, narrow polydispersity and excellent functional group tolerance. The process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling. We have also observed that the process is not sensitive to scale-up, which is essential for its future translation from laboratory research to industrial applications.

  • Compound

    ((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    (((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    bis(4-((tert-butyldimethylsilyl)oxy)phenyl)diphenylmethane

  • Compound

    3,3-bis(4-((tert-butyldimethylsilyl)oxy)phenyl)isobenzofuran-1(3H)-one

  • Compound

    2,7-bis((tert-butyldimethylsilyl)oxy)naphthalene

  • Compound

    ((oxybis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    4,4'-bis((tert-butyldimethylsilyl)oxy)-1,1'-biphenyl

  • Compound

    (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    ((propane-2,2-diylbis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    ((cyclohexane-1,1-diylbis(4,1-phenylene))bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    ((5-methoxy-1,3-phenylene)bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    ((5-(prop-2-yn-1-yloxy)-1,3-phenylene)bis(oxy))bis(tert-butyldimethylsilane)

  • Compound

    4-(2-(4-((tert-butyldimethylsilyl)oxy)phenyl)propan-2-yl)benzenesulfonic hypofluorous anhydride

  • Compound

    propane-2,2-diylbis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    (perfluoropropane-2,2-diyl)bis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    (diphenylmethylene)bis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    (3-oxo-1,3-dihydroisobenzofuran-1,1-diyl)bis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    naphthalene-2,7-diyl bis(sulfurofluoridate)

  • Compound

    oxybis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    [1,1'-biphenyl]-4,4'-diyl bis(sulfurofluoridate)

  • Compound

    (9H-fluorene-9,9-diyl)bis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    propane-2,2-diylbis(2,6-dimethyl-4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    cyclohexane-1,1-diylbis(4,1-phenylene) bis(sulfurofluoridate)

  • Compound

    propane-1,3-disulfonyl difluoride

  • Compound

    butane-1,4-disulfonyl difluoride

  • Compound

    pentane-1,5-disulfonyl difluoride

  • Compound

    1,1,2,2,3,3,4,4-octafluorobutane-1,4-disulfonyl difluoride

  • Compound

    [1,1'-biphenyl]-4,4'-disulfonyl difluoride

  • Compound

    tetramethylammonium hydrogendifluoride

  • Compound

    tetrabutylammonium hydrogendifluoride

  • Compound

    1,3-diisopropylimidazolium hydrogendifluoride

  • Compound

    1-methyl-3-butylimidazolium hydrogendifluoride

  • Compound

    tris(dimethylamino)sulfonium hydrogendifluoride

  • Compound

    hexamethylguanidinium hydrogendifluoride

  • Compound

    N-(1,3-dimethylimidazolidin-2-ylidene)-N-methylmethanaminium hydrogendifluoride

  • Compound

    tetraphenylarsonium hydrogendifluoride

  • Compound

    tributyl(hexadecyl)phosphonium hydrogendifluoride

  • Compound

    1,1,1-triphenyl-N-(triphenyl-λ5-phosphaneylidene)-λ5-phosphaniminium hydrogendifluoride

  • Compound

    1,1,1-triphenyl-N-(triphenyl-λ5-phosphaneylidene)-λ5-phosphaniminium dihydrogentrifluoride

  • Compound

    1,1,1-triphenyl-N-(triphenyl-λ5-phosphaneylidene)-λ5-phosphaniminium trihydrogentetrafluoride

  • Compound

    1,1,1-triphenyl-N-(triphenyl-λ5-phosphaneylidene)-λ5-phosphaniminium tetrahydrogenpentafluoride

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Acknowledgements

Financial support was provided by the National Science Foundation (CHE-1610987 to K.B.S.) and the National Institutes of Health (GM093282 to P.W.). Part of the work was carried out as a user project at the Molecular Foundry, which was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. B.G. is grateful for the postdoctoral fellowship support from the Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Science (CAS), Pharmaron and Zhejiang Medicine. J.D. is grateful for the One Hundred Talents Program supported by SIOC, CAS. J.D. is financially supported by the Strategic Priority Research Program of the CAS (XDB200203) and the National Natural Science Foundation of China (21672240). We thank P. Dawson at The Scripps Research Institute (TSRI) for the anhydrous HF experiment. We also thank S. Li and C. J. Hawker at University of California, Santa Barbara, Q. Xu and B. Wu at Soochow University, S. Li and H. Wang at TSRI for helpful discussions on this project.

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Affiliations

  1. Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, USA

    • Bing Gao
    • , Qinheng Zheng
    •  & K. Barry Sharpless
  2. Department of Molecular Medicine, The Scripps Research Institute, La Jolla, California 92037, USA

    • Linda Zhang
    •  & Peng Wu
  3. College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou, Nano Science and Technology, Soochow University, Suzhou 215123, China

    • Feng Zhou
    •  & Jianmei Lu
  4. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • Liana M. Klivansky
    •  & Yi Liu
  5. Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry Shanghai 200032, China

    • Jiajia Dong
    •  & K. Barry Sharpless

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Contributions

K.B.S. and P.W. led the project. J.D. and B.G. designed the experiments. B.G., J.D. and L.Z. carried out the experiments. F.Z., L.M.K., J.L. and Y.L. collected and analysed the TGA and DSC data of all polymers and provided helpful suggestion on the project. B.G. wrote the manuscript. P.W., Q.Z., J.D., Y.L. and K.B.S. edited the manuscript.

Competing interests

A patent application covering this work has been filed by TSRI (US patent application no. 62/182755, International patent application no. PCT/US2016/038701).

Corresponding authors

Correspondence to Jiajia Dong or Peng Wu or K. Barry Sharpless.

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DOI

https://doi.org/10.1038/nchem.2796

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