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Rapid and chemoselective imidation of sulfides in aqueous buffer enabled by a novel guanidine-derived N-O reagent

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Abstract

Herein we report the facile synthesis of a series of novel N-O reagents and identify N′-di-Boc-N″-[(mesitylsulfonyl)oxy]-guanidine as an efficient imidating reagent. This reagent is synthetically scalable and bench-stable, yet it shows unprecedented reactivity and chemoselectivity towards S(II) in buffer/hexafluoroisopropanol (HFIP) system, to generate a new class of N-guanyl sulfilimines. Further transformation of N-guanyl sulfilimines to N-guanyl sulfoximines provides us a chance to investigate these rarely reached compounds, which are shown to be versatile precursors to a variety of N-heterocyclic and NH-sulfoximines. Our work provides an addition to the tool box of both sulfur imidation and guanidine synthesis, especially for the need of rapid and selective modifications of sulfur(II) center under biocompatible conditions.

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Acknowledgements

This work was supported by the Ministry of Science and Technology of China, Major State Basic Research Development Program of China (2023YFA1506500, 2021YFF0701704), and Shanghai Pilot Program for Basic Research, Shanghai Jiao Tong University (21TQ1400223). Prof. J. Dong thank WLA Laboratories for the financial support.

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Authors and Affiliations

  1. Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, 200032, China

    Hanzheng Li

  2. Institute of Translational Medicine, National Facility for Translational Medicine (Shanghai), Shanghai Jiao Tong University, Shanghai, 200240, China

    Long Xu & Jiajia Dong

  3. School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China

    Jiajia Dong

  4. Shanghai Artificial Intelligence Laboratory, Shanghai, 200232, China

    Jiajia Dong

Authors
  1. Hanzheng Li
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  2. Long Xu
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  3. Jiajia Dong
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Corresponding authors

Correspondence to Long Xu or Jiajia Dong.

Ethics declarations

Conflict of interest The authors declare the following competing financial interests: has filed a Chinese patent application (CN202310318743.2) on this reagent and its applications.

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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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Li, H., Xu, L. & Dong, J. Rapid and chemoselective imidation of sulfides in aqueous buffer enabled by a novel guanidine-derived N-O reagent. Sci. China Chem. (2024). https://doi.org/10.1007/s11426-023-1947-8

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  • DOI: https://doi.org/10.1007/s11426-023-1947-8

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