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Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent ·CF2H, CF2H+, and:CF2 reactivities

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Abstract

Development of practical and versatile electrophilic difluoromethylating reagent is still a grand challenge so far due to its inherent instability or low reactivity. Herein, we report the design and synthesis of difluoromethyl phenoxathiinium tetrafluoroborate (PT-CF2H+BF4−) as a novel difluoromethylating reagent, which proves to be a bench-stable, general, powerful and versatile reagent with divergent ·CF2H, CF2H+, and:CF2 reactivities. Making use of this reagent, we demonstrated a vast array of difluoromethyl radical transfer reactions via diverse pathways involving photocatalyst-free visible-light induction, visible-light photoredox catalysis and visible-light mediation single electron transfer of EDA complex. Moreover, the green and highly effective CF2H+ and:CF2 transfer reactions were also readily accomplished.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (92056201), Guangdong Basic and Applied Basic Research Foundation (2023A1515011008), and Shenzhen Science and Technology Program (the Stable Support Plan Program 20220808130958001). We sincerely thank Professor Henry N.C. Wong at The Chinese University of Hong Kong (Shenzhen) for his useful discussion and kind help, and thank the Instrumental Analysis Center of Shenzhen University for its analytical work.

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Authors and Affiliations

  1. School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen, 518055, China

    Yuan-Qing Gu, Hong-Xin Long, Dan-Dan Zhang, Mei-Feng Ruan & Guo-Kai Liu

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  1. Yuan-Qing Gu
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  2. Hong-Xin Long
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Correspondence to Guo-Kai Liu.

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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_2023_1862_MOESM1_ESM.pdf

Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent ·CF2H, CF2H+, and:CF2 reactivities

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Gu, YQ., Long, HX., Zhang, DD. et al. Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent ·CF2H, CF2H+, and:CF2 reactivities. Sci. China Chem. 67, 953–962 (2024). https://doi.org/10.1007/s11426-023-1862-x

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