Communication
ChemComm
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of electron-withdrawing NO2 or CF3-substituted products 3j, 3k,
3p and 3t, suggests that the Cl–F exchange reaction proceeds in
an intermolecular concerted process such as I-1, I-2 and I-3
rather than via a nucleophilic attack by naked fluoride.8d, f
A novel approach for the silver-induced self-immolative Cl–F
exchange fluorination of arylsulfur chlorotetrafluorides Ar-SF4Cl 2
to arylsulfur pentafluorides Ar-SF5 3 was achieved. The Cl–F
exchange fluorination of 2 is an important step for the final stage
of the synthesis of Ar-SF5 3 and is highly dependent on the choice
of the fluoride source. Our present approach does not require any
external fluorides for the Cl–F exchange reaction. Rather, the
reaction proceeds in a very unique self-immolative fashion. The
substrate and functional group generality are high and heteroaryl
SF4Cl such as pyridine is also tolerated, and moderate to good
yields are obtained. Due to the self-immolative nature of the
reaction, yields cannot reach 100%, while some yields are indeed
higher than those reported using exogenous fluorides. An
environmentally benign solvent, Solkanes 365/227, is applicable
to this process.
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This research is partially supported by the Tokyo Chemical
Industry Foundation, the Pesticide Science Society of Japan, and
the Advanced Catalytic Transformation (ACT-C, JPMJCR12Z7)
from the JST Agency. B. Cui was supported by a CSC fellowship.
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