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C–H fluorination

U can fluorinate unactivated bonds

Nature Chemistry volume 8, pages 822–823 (2016)Cite this article

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Introducing C–F bonds into organic molecules is a challenging task, particularly through C–H activation methods. Now, a uranium-based photocatalyst turns traditional selectivity rules on their heads and fluorinates unfunctionalized alkane Csp3–H bonds, even in the presence of C–H bonds that are typically more reactive.

The formation of C–F bonds is commonly associated with large kinetic barriers that, despite the high C–F bond energy, generally necessitate the use of fluorinating reagents with high oxidation potentials. Although F2 gas is sufficiently reactive to generate carbon-centred radicals from alkanes, bench-stable electrophilic fluorinating reagents such as F–TEDA and NFSI typically do not react with alkanes. However, using additional reagents or catalysts capable of generating alkyl radicals can facilitate aliphatic fluorination. In 2012, Groves and co-workers set a standard for aliphatic C–H fluorination by intercepting an intermediate in the radical rebound mechanism of a manganese porphyrin catalyst1. According to the proposed mechanism, C–H abstraction by a manganese-oxo complex is followed by AgF-induced exchange of the resulting hydroxide ligand for a fluoride ligand that is subsequently incorporated into the alkyl fluoride product.

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Figure 1: Preliminary results for selectivity towards traditionally less reactive C–H bonds.

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Authors and Affiliations

  1. Tobias Ritter and Constanze Neumann are at the Department for Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA,

    Constanze N. Neumann & Tobias Ritter

  2. Tobias Ritter is also at the Max Planck Institute for Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Muelheim, Germany,

    Tobias Ritter

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  1. Constanze N. Neumann
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  2. Tobias Ritter
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Correspondence to Tobias Ritter.

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Neumann, C., Ritter, T. U can fluorinate unactivated bonds. Nature Chem 8, 822–823 (2016). https://doi.org/10.1038/nchem.2604

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