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Understanding how charge-charge interaction affects the stereochemistry of enamine fluorination by chiral primary amine catalysis

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Abstract

Electrostatic interaction, especially electrostatic attraction, usually plays critical roles in controlling the reactivity and selectivity in catalytic transformations; however, the like-charge repulsion, which is ubiquitous in physical systems, is rarely applied in reaction control. Herein we disclosed an unexpected like-charge repulsion induced enantio-control mode in primary aminecatalyzed fluorination reactions with 1-fluoro-2,4,6-trimethylpyridinium triflate. The ionic reaction works favorably in both highly polar (methanol) and non-polar (hexane) solvents, a seldom observed phenomenon in asymmetric catalysis. Erying plot analysis showed that an inversion temperature existed in MeOH, which was explained by the solvent-solute cluster model under different temperatures. Density functional theory (DFT) study and energy decomposition analysis (EDA) verified that the like-charge repulsion takes effect in polar solvent methanol, while in nonpolar solvents, the steric repulsion associated with ion-pair was found to be the major effect for the observed enantioselectivity.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22373056, 22031006), the Haihe Laboratory of Sustainable Chemical Transformations (YYJC202113), and the National Science & Technology Fundamental Resource Investigation Program of China (2018FY201200). L.Z. was supported by the National Program of Top-notch Young Professionals.

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Authors and Affiliations

  1. Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Yanfang Han, Kai Yang, Long Zhang, Sanzhong Luo & Jin-Pei Cheng

  2. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, China

    Long Zhang, Sanzhong Luo & Jin-Pei Cheng

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  1. Yanfang Han
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  2. Kai Yang
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  3. Long Zhang
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  4. Sanzhong Luo
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Correspondence to Long Zhang or Sanzhong Luo.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://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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11426_2023_1746_MOESM1_ESM.pdf

Understanding How Charge-charge Interaction Affects the Stereochemistry of Enamine Fluorination by Chiral Primary Amine Catalysis

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Han, Y., Yang, K., Zhang, L. et al. Understanding how charge-charge interaction affects the stereochemistry of enamine fluorination by chiral primary amine catalysis. Sci. China Chem. 66, 2828–2835 (2023). https://doi.org/10.1007/s11426-023-1746-7

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  • DOI: https://doi.org/10.1007/s11426-023-1746-7

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