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Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes

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Abstract

The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIV-functionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center (N–R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22001065), the Science and Technology Foundation of Hunan Province (2021JJ30090), Guangdong Provincial Key Laboratory of Catalysis (2020B121201002), and Shenzhen Science and Technology Program (KQTD20210811090112004). Computational work was supported by Center for Computational Science and Engineering at SUSTech, and the CHEM high-performance supercomputer cluster (CHEM-HPC) located at the Department of Chemistry, SUSTech.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Institute of Chemical Biology and Nanomedicine, Hunan University, Changsha, 410082, China

    Xi Zou, Gao-lin Li, Qian Liang, Yanhua Ouyang, Binghe Yang & Bing Gao

  2. Department of Chemistry and Shenzhen Grubbs Institute, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, 518055, China

    Boming Shen & Peiyuan Yu

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  1. Xi Zou
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Correspondence to Peiyuan Yu or Bing Gao.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://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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Zou, X., Shen, B., Li, Gl. et al. Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes. Sci. China Chem. 67, 928–935 (2024). https://doi.org/10.1007/s11426-023-1842-8

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  • DOI: https://doi.org/10.1007/s11426-023-1842-8

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