• Open Access

Cation versus Radical: Studies on the C/O Regioselectivity in Electrophilic Tri-, Di- and Monofluoromethylations of β-Ketoesters

Authors

  • Yu-Dong Yang,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Xu Lu,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Guokai Liu,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Etsuko Tokunaga,

    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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  • Dr. Seiji Tsuzuki,

    Corresponding author
    1. National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan)
    • National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan)
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  • Prof. Norio Shibata

    Corresponding author
    1. Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
    • Department of Frontier Materials, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555 (Japan)
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Abstract

original image

Fluoromethylation. The C/O regioselectivity of β-ketoesters with fluorinated methylsulfoxinium salts 2 is discussed. Trifluoromethylation involves the formation of a more cationic species represented by +CF3 to provide C-alkylated products, while monofluoromethylation possibly proceeds involving a more radical-like species such as .CFH2 to give O-alkylated species. Difluoromethylation could involve both cationic and radical species, which afford a mixture of C and O isomers.

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