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Para-selective borylation of monosubstituted benzenes using a transient mediator

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Abstract

Herein, we conceptualized a transient mediator approach that has the capability of para-selective C-H functionalization of monosubstituted aromatics. This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride. Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate. The versatility of this approach was demonstrated via para-borylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.

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Acknowledgements

This work was supported by Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry, the National Natural Science Foundation of China (21890722, 21702109, 11811530637), the Natural Science Foundation of Tianjin City (18JCYBJC21400) and the Fundamental Research Funds for the Central Universities (63191515, 63196021, 63191523).

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Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Shanghai, 200032, China

    Jie Wu, Xiao-Yue Chen, Yichen Wu, Daoming Wang & Peng Wang

  2. CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, Shanghai, 200032, China

    Peng Wang

  3. State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China

    Zengwei Wang & Qian Peng

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  1. Jie Wu
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  2. Zengwei Wang
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  3. Xiao-Yue Chen
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  4. Yichen Wu
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  5. Daoming Wang
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  7. Peng Wang
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Correspondence to Qian Peng or Peng Wang.

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Wu, J., Wang, Z., Chen, XY. et al. Para-selective borylation of monosubstituted benzenes using a transient mediator. Sci. China Chem. 63, 336–340 (2020). https://doi.org/10.1007/s11426-019-9652-x

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