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Electric-field-controlled highly regioselective thiocyanation of N-containing heterocycles

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Abstract

Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners. External electric fields (EEFs) can influence the reactivity and selectivity of the substrate by causing directional adsorption. However, scalable and efficient techniques for using EEFs as “smart catalysts” have been lacking, hindering their application. In this study, we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer (EDL) theory. This approach led to moderate to good yields of the corresponding C7-thiocyanation products. DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones, allowing the C7-thiocyanation to proceed via a radical reaction mechanism. Additionally, the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties. Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21172200, 21302172), the Basic Research Training Project of Zhengzhou University (JC2020053021). This work was also supported by the National Research Foundation of Korea (CRI Project No. 2018R1A3B1052702 for Jong Seung Kim).

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Authors and Affiliations

  1. Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, College of Chemistry, Zhengzhou University, Zhengzhou, 450052, China

    Ming Gong, Qian Wu, Jung Keun Kim, Mengmeng Huang, Yabo Li & Yangjie Wu

  2. Department of Chemistry, Korea University, Seoul, 02841, Korea

    Jong Seung Kim

Authors
  1. Ming Gong
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  2. Qian Wu
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  3. Jung Keun Kim
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  4. Mengmeng Huang
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  5. Yabo Li
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  6. Yangjie Wu
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  7. Jong Seung Kim
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Correspondence to Mengmeng Huang, Yabo Li or Jong Seung Kim.

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Supporting information The supporting information is available online at chem.scichina.com and link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Gong, M., Wu, Q., Kim, J.K. et al. Electric-field-controlled highly regioselective thiocyanation of N-containing heterocycles. Sci. China Chem. 67, 1263–1269 (2024). https://doi.org/10.1007/s11426-023-1885-2

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