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Enantioselective sulfur(VI) fluoride exchange reaction of iminosulfur oxydifluorides

Nature Chemistry volume 16, pages 353–362 (2024)Cite this article

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Abstract

Linkage chemistry and functional molecules derived from the stereogenic sulfur(VI) centre have important applications in organic synthesis, bioconjugation, drug discovery, agrochemicals and polymeric materials. However, existing approaches for the preparation of optically active S(VI)-centred compounds heavily rely on synthetic chiral S(IV) pools, and the reported linkers of S(VI) lack stereocontrol. A modular assembly method, involving sequential ligand exchange at the S(VI) centre with precise control of enantioselectivity, is appealing but remains elusive. Here we report an asymmetric three-dimensional sulfur(VI) fluoride exchange (3D-SuFEx) reaction based on thionyl tetrafluoride gas (SOF4). A key step involves the chiral ligand-induced enantioselective defluorinative substitution of iminosulfur oxydifluorides using organolithium reagents. The resulting optically active sulfonimidoyl fluorides allow for further stereospecific fluoride-exchange by various nucleophiles, thereby establishing a modular platform for the asymmetric SuFEx ligation and the divergent synthesis of optically active S(VI) functional molecules.

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Fig. 1: Functional molecules and linkers carrying a stereogenic SVI centre.
Fig. 2: The mechanistic study and discussion.
Fig. 3: Calculated Gibbs free energy profile and plausible stereochemical modes.
Fig. 4: Chemoselective transformations.

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Data availability

All relevant data supporting the findings of this study, including experimental procedures and compound characterization, are available within the article and its supplementary information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2128746 (1t), 2128749 ((R)-3ab), 2242977 ((S)-4b), 2128751 ((R)-4c) and 2128755 ((S)-4e). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

Financial support was provided by National Natural Science Foundation of China (22001065 to B.G., 22122104 to X.-S.X., 22193012 to X.-S.X. and 21933004 to X.-S.X.), the Science and Technology Foundation of Hunan Province (2021JJ30090 to B.G.), the Ministry of Science and Technology of China (2021YFF0701700 to X.-S.X. and 2021YFF0701704 to J.D.), J.D. is also thankful for the financial support from Shanghai Pilot Program for Basic Research, Shanghai Jiao Tong University and the WLA Laboratories. B.G. thanks K. B. Sharpless, P. Wu and J. Cappiello at Scripps Research for their generous support and helpful discussion.

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Author notes

  1. These authors contributed equally: Zhiyuan Peng, Shoujun Sun, Meng-Meng Zheng.

Authors and Affiliations

  1. State Key Laboratory of Chemo/BioSensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Biomacromolecular Chemical Biology, Hunan University, Changsha, China

    Zhiyuan Peng, Yangyang Li & Bing Gao

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

    Shoujun Sun, Xixi Li & Jiajia Dong

  3. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, China

    Meng-Meng Zheng & Xiao-Song Xue

  4. School of Chemistry, Sun Yat-Sen University, Guangzhou, China

    Suhua Li

  5. Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China

    Xiao-Song Xue

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Contributions

B.G. and J.D. conceived and directed the project. Z.P., S.S., Y.L., X.L., S.L. and B.G. conducted the experiments. M.-M.Z. and X.-S.X. conducted the DFT calculations. B.G. wrote the manuscript with the input from all authors.

Corresponding authors

Correspondence to Xiao-Song Xue, Jiajia Dong or Bing Gao.

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Nature Chemistry thanks Xuefeng Jiang, Patrick Melvin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

The supplementary information file contains 12 sections, covering the experimental procedure, synthesis and characterization data, NMR spectra, X-ray crystallographic data, DFT calculation and references.

Supplementary Data 1

Crystallographic data for compound (R)-3ab; CCDC reference 2128749.

Supplementary Data 2

Crystallographic data for compound (R)-4c; CCDC reference 2128751.

Supplementary Data 3

Crystallographic data for compound (S)-4b; CCDC reference 2242977.

Supplementary Data 4

Crystallographic data for compound (S)-4e; CCDC reference 2128755.

Supplementary Data 5

Crystallographic data for compound 1t; CCDC reference 2128746.

Supplementary Data 6

Structure factors for compound (R)-3ab; CCDC reference 2128749.

Supplementary Data 7

Structure factors for compound (R)-4c; CCDC reference 2128751.

Supplementary Data 8

Structure factors for compound (S)-4b; CCDC reference 2242977.

Supplementary Data 9

Structure factors for compound (S)-4e; CCDC reference 2128755.

Supplementary Data 10

Structure factors for compound 1t; CCDC reference 2128746.

Supplementary Data 11

Computational data for DFT calculations.

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Peng, Z., Sun, S., Zheng, MM. et al. Enantioselective sulfur(VI) fluoride exchange reaction of iminosulfur oxydifluorides. Nat. Chem. 16, 353–362 (2024). https://doi.org/10.1038/s41557-024-01452-w

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