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Switching from 2-pyridination to difluoromethylation: ligand-enabled nickel-catalyzed reductive difluoromethylation of aryl iodides with difluoromethyl 2-pyridyl sulfone

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Abstract

The divergent reductive cross-coupling with an ambident electrophile is rare. Previously, we demonstrated a nickel-catalyzed reductive 2-pyridination of aryl iodides with difluoromethyl 2-pyridyl sulfone (2-PySO2CF2H) via selective C(sp2)–S bond cleavage of the sulfone by using a phosphine ligand. In this communication, we report a novel nickel-catalyzed reductive coupling of aryl iodides and 2-PySO2CF2H reagent, which constitutes a new method for aromatic difluoromethylation. The use of a tridentate terpyridine ligand is pivotal for the selective C(sp3)–S bond cleavage of the sulfone. This method employs readily available nickel catalyst and 2-PySO2CF2H as the difluoromethylation reagent, providing a facile access to difluoromethylarenes under mild reaction conditions without pre-generation of arylmetal reagents.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2021YFF0701700), the National Natural Science Foundation of China (22271299, 22261132514), the Natural Science Foundation of Shandong Province (ZR2021LFG006), and the State Key Laboratory of Fluorine-Containing Functional Membrane Materials. Shandong Dongyue Polymer Materials Co. Ltd. is acknowledged for a gift of difluoromethyl 2-pyridyl sulfone (2-PySO2CF2H).

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Authors and Affiliations

  1. Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, 200032, China

    Wei Du, Qinyu Luo, Zhiqiang Wei, Xiu Wang, Chuanfa Ni & Jinbo Hu

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  1. Wei Du
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  2. Qinyu Luo
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  3. Zhiqiang Wei
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  4. Xiu Wang
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  5. Chuanfa Ni
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  6. Jinbo Hu
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Correspondence to Jinbo Hu.

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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_1791_MOESM1_ESM.pdf

Switching from 2-Pyridination to Difluoromethylation: Ligand-Enabled Nickel-Catalyzed Reductive Difluoromethylation of Aryl Iodides with Difluoromethyl 2-Pyridyl Sulfone

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Du, W., Luo, Q., Wei, Z. et al. Switching from 2-pyridination to difluoromethylation: ligand-enabled nickel-catalyzed reductive difluoromethylation of aryl iodides with difluoromethyl 2-pyridyl sulfone. Sci. China Chem. 66, 2785–2790 (2023). https://doi.org/10.1007/s11426-023-1791-3

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  • DOI: https://doi.org/10.1007/s11426-023-1791-3

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