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Dissolving metal reduction K metal-crown ether-toluene system for reductive defluorination

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Abstract

Toluene radical anion, generated by dissolving potassium metal in toluene by the assistance of dicyclohexano-18-crown-6, has been proved to be especially effective for reductive removal of fluorine atom from unactivated alkyl fluorides that resist common reduction conditions. Stereochemical and mechanistic aspects of the present method is discussed. In connection with the preparation of substrates the effect of dipolar aprotic solvents on the nucleophilic fluorination with potassium fluoride/dicyclohexano-18-crown-6 system was also examined, and sulfolane or N,N-dimethyl formamide was shown to be a solvent of choice.

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Authors and Affiliations

  1. Riken (The Institute of Physical and Chemical Research), 2-1 Hirosawa, 351-01, Wako, Saitama, Japan

    Tomihiko Ohsawa & Takeshi Oishi

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  1. Tomihiko Ohsawa
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  2. Takeshi Oishi
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T. Ohsawa, T. Takagaki, A. Haneda and T. Oishi,Tetrahedron Lett.,1981, 2583.

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Ohsawa, T., Oishi, T. Dissolving metal reduction K metal-crown ether-toluene system for reductive defluorination. Journal of Inclusion Phenomena 2, 185–194 (1984). https://doi.org/10.1007/BF00663255

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