A Tandem Anion and Radical Tetrafluoroethylene Equivalent
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getically more favorable than transition state B for the cis-
5 because it does not involve unfavorable 1,3-diaxial inter-
actions between the fluorine atom and the CHR3 group.
Conclusions
In conclusion, we have developed PhSCF2CF2SiMe3 (1)
as a tandem anion and radical tetrafluoroethylene equiva-
lent for introduction of –CF2CF2H and –CF2CF2– moie-
ties. Compound 1 underwent fluoride-initiated nucleophilic
addition to aldehydes and activated ketones, providing (af-
ter hydrolysis of the intermediate TMS-ether) substituted
2,2,3,3-tetrafluoro-3-phenylsulfanylpropan-1-ols (2) in high
yields. Compounds 2 underwent reduction under free radi-
cal conditions to substituted 2,2,3,3-tetrafluoropropan-1-
ols (3) in moderate to high yields, demonstrating the appli-
cation of 1 as a tetrafluoroethyl carbanion equivalent.
Compounds 2 were converted into allyl ethers 4 and cy-
clized under free radical conditions to give substituted tet-
rafluorotetrahydrofurans 5 in a 76:24 to 89:11 trans/cis ratio
in moderate to good yields.
[11] Me3SiCF2CF2SiMe3 together with Me3SiCF2SiMe3 have been
prepared by electrolysis of Me3SiCF2Cl in the presence of Me3-
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spectra of compounds 3–5.
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Acknowledgments
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[18] Also known as R-114B2 or Halon 2402, a dense (d =
2.18 gcm–3), volatile (b.p. 47 °C), colorless liquid, which is used
in fire suppression systems, mainly in military land vehicles,
naval vessels, and aircrafts. Large-scale production of
Halon 2402 has been banned since 1994 in accordance with
obligations under the Montreal Protocol on Substances that
Deplete the Ozone Layer. However, the compound is still com-
mercially available for research purposes, and multikilogram
quantities can be obtained from specialized Halon 2402 storage
facilities.
[19] Tetrabutylammonium triphenyldifluorosilicate.
[20] CCDC-824772 (for 5a) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Support of this work by the Academy of Sciences of the Czech
Republic (Research Plan AVZ40550506) and the Grant Agency of
the Czech Republic (207/11/0421) is gratefully acknowledged.
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Received: May 12, 2011
Published Online: July 12, 2011
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Eur. J. Org. Chem. 2011, 4528–4531
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