Despite the growing interest in the synthesis of fluorinated organic compounds, few methods are able to incorporate fluoride ion directly into alkyl C-H bonds. Here, we report the C(sp 3)-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, LCuF, along with its chloride and bromide analogs, LCuCl and LCuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized. While all three copper(III) halide complexes capture carbon radicals efficiently to afford C(sp 3)-halogen bonds, LCuF is two orders of magnitude more efficient at hydrogen atom abstraction (HAA) than LCuCl and LCuBr. Alongside reported kinetic data for other LCu(III) species, we established a positive correlation between ligand basicity and the rate of HAA. The capability of LCuF to perform both hydrogen atom abstraction and radical capture was leveraged to enable fluorination of allylic and benzylic C-H bonds and α-C-H bonds of ethers at room temperature.
<p>Despite the growing interest in the synthesis of fluorinated organic compounds, few methods are able to incorporate fluoride ion directly into alkyl C-H bonds. Here, we report the C(sp<sup>3</sup>)-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, <b>L</b>CuF, along with its chloride and bromide analogs, <b>L</b>CuCl and <b>L</b>CuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized. While all three copper(III) halide complexes capture carbon radicals efficiently to afford C(sp<sup>3</sup>)-halogen bonds, <b>L</b>CuF is two orders of magnitude more efficient at hydrogen atom abstraction (HAA) than <b>L</b>CuCl and <b>L</b>CuBr. Alongside reported kinetic data for other <b>L</b>Cu(III) species, we established a positive correlation between ligand basicity and the rate of HAA. The capability of <b>L</b>CuF to perform both hydrogen atom abstraction and radical capture was leveraged to enable fluorination of allylic and benzylic C-H bonds and α-C-H bonds of ethers at room temperature.</p>
Despite the growing interest in the synthesis of fluorinated organic compounds, few methods are able to incorporate fluoride ion directly into alkyl C-H bonds. Here, we report the C(sp 3 )-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, LCuF, along with its chloride and bromide analogs, LCuCl and LCuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized. While all three copper(III) halide complexes capture carbon radicals efficiently to afford C(sp 3 )-halogen bonds, LCuF is two orders of magnitude more efficient at hydrogen atom abstraction (HAA) than LCuCl and LCuBr. Alongside reported kinetic data for other LCu(III) species, we established a positive correlation between ligand basicity and the rate of HAA. The capability of LCuF to perform both hydrogen atom abstraction and radical capture was leveraged to enable fluorination of allylic and benzylic C-H bonds and α-C-H bonds of ethers at room temperature.Carbon-fluorine bonds are becoming increasingly prevalent in pharmaceuticals and agrochemicals. 1 The value of fluorinated compounds in these applications stems from their enhancement of lipophilicity, metabolic stability, and receptor binding affinity. 2
The transfer of PtCl62− ions into the organic phase facilitated by TOA+ is the very first step in the Brust‐Schiffrin (BS) two‐phase synthesis of monolayer protected Pt nanoparticles. However, the stoichiometry between TOA+ and PtCl62− during the facilitated transfer process is still unknown. In this paper, a hemispherical micro‐liquid/liquid interface, which is formed between a PtCl62− aqueous filled micropipette and an organic phase, has been employed to study the stoichiometry of TOA+ facilitated transfer of PtCl62−. Due to the even diffusion field at the hemispherical micro‐liquid/liquid interface, the theoretical i‐V curve for TOA+ facilitated transfer of PtCl62− can be derived in a simple way. By simulating the theoretical i‐V curve to the experimental voltammogram, the stoichiometry of TOA+ facilitated transfer of PtCl62− was evaluated to be 8.
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