ACS Catalysis
Research Article
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and good functional group tolerance. This novel nickel catalyst
also exhibits powerful efficiency in the gram-scale synthesis of
thienyl-2,3,5,6-tetrafluorophenyl units, as well as in the
preparation of symmetry and unsymmetry polyfluorinated
polyaryls, which represent key components in materials science.
On the basis of our studies, polyfluorinated magnesium
species generated in situ from corresponding simple poly-
fluoroarenes have their own advantages as KTC coupling
partners, including (1) their efficient transmetalation rate, (2)
their good functional group tolerance even at room temper-
ature, (3) interestingly the fact they are not likely to form
homocoupling byproducts and engage in C−F bond activation,
and (4) most importantly their potential coupling partners in
the large-scale monoarylation of fluoroarenes. These unique
properties make the current ArFn-MgX-involved Ni-catalyzed
KTC coupling strategy complementary in the synthesis of
various important polyfluorobiaryls. Employing polyfluorinated
magnesium species to synthesize other interesting polyfluor-
oaromatics is currently under investigation.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
Experimental procedure and characterization data (PDF)
1
Copies of H, 13C, 19F, and 31P NMR spectra of all new
(13) For transition metal-catalyzed C−F bond activation, see reviews:
(a) Amii, H.; Uneyama, K. Chem. Rev. 2009, 109, 2119−2183.
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X-ray data for compound ArF4-MgCl (CIF)
X-ray data for compound 4 (CIF)
X-ray data for compound 18 (CIF)
X-ray data for compound 21 (CIF)
AUTHOR INFORMATION
Corresponding Author
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(14) Lanni, E. L.; McNeil, A. J. J. Am. Chem. Soc. 2009, 131, 16573−
16579.
(15) (a) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881−
̈
ORCID
1886. (b) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem.
Notes
The authors declare no competing financial interest.
Soc. Rev. 2008, 37, 320−330. (c) Wang, J.; San
́
chez-Rosello,
́
M.;
Acena, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok,
̃
V. A.; Liu, H. Chem. Rev. 2014, 114, 2432−2506. (d) Zhou, Y.; Wang,
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ACKNOWLEDGMENTS
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We thank the National Natural Science Foundation of China
(21302115), the Natural Science Foundation of Shaanxi
Province (2015JM2064), the Fundamental Research Funds
for the Central Universities (GK201706006), and Funded
Projects for the Academic Leaders and Academic Backbones,
Shaanxi Normal University (16QNGG009), for financial
support.
(16) Babudri, F.; Farinola, G. M.; Naso, F.; Ragni, R. Chem. Commun.
2007, 1003−1022.
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C.; Lindval, M.; Atallah, G.; Ding, Y.; Mathur, M.; McBride, C.; Beans,
E. L.; Muller, K.; Tamez, V.; Zhang, Y.; Huh, K.; Feucht, P.;
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