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The synergism of sequential paired electrosynthesis with halogen bonding activation for the cyclization of organochlorides with olefins

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Abstract

Reported herein is the design of a new catalytic paradigm by synergistically combining sequential paired electrosynthesis with halogen-bonding (XB) activation for the cyclization of organochlorides with olefins. This dual activation strategy enables rapid access to densely functionalized 2-alkylidene-tetrahydrofurans with exclusive Z-selectivities, which are challenging to be synthesized by other methods. 4,4′-Di-tert-butyl-2,2′-bipyridine (dtbbpy) showed an unprecedented reactivity as a XB acceptor to activate C-Cl bond by shifting its reduction potential positively by 220 mV. Distinctly different from previous electro-reductions of C-Cl bonds relying upon high electrode potentials or matched redox properties between mediators and organochlorides, the XB activator employed herein has no limit on the abovementioned redox property matching but can lower the applied electrode potentials The decreased operating potential allows broad functional group tolerance, which was highlighted by the late-stage functionalization of 11 examples of drugs and natural products-derived alkenes.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21871019, 22171015), Beijing Municipal Education Committee Project (KZ202110005003, KM202110005006), and Beijing Natural Science Foundation (2222003). We also extend our thanks to the Large-scale Instruments and Equipments Sharing Platform of Beijing University of Technology for NMR experiments.

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Authors and Affiliations

  1. Faculty of Environment and Life, Beijing University of Technology, Beijing, 100124, China

    Fei Lian, Kun Xu & Chengchu Zeng

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  1. Fei Lian
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  2. Kun Xu
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  3. Chengchu Zeng
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Correspondence to Kun Xu or Chengchu Zeng.

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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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11426_2022_1410_MOESM1_ESM.pdf

The Synergism of Sequential Paired Electrosynthesis with Halogen Bonding Activation for the Cyclization of Organochlorides with Olefins

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Lian, F., Xu, K. & Zeng, C. The synergism of sequential paired electrosynthesis with halogen bonding activation for the cyclization of organochlorides with olefins. Sci. China Chem. 66, 540–547 (2023). https://doi.org/10.1007/s11426-022-1410-6

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