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tist (16XD1404600).
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REFERENCES
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Based on the experiments above and literature preceꢀ
dents,20aꢀb,i,21 a plausible catalytic cycle is proposed in Scheme
8. The active Ru complex A is firstly formed from substrate 1a
with Ru3(CO)12 via CArꢀH activation step. Subsequent electroꢀ
philic attack of the para-carbon relative to the RuꢀCAr σꢀbond
occurs to generate species B.21b In this process, nitrogen dioxꢀ
ide radical (NO2•) is originated through a silverꢀmediated radiꢀ
cal process.20a,i An anion exchange between Cu(NO3)2 and
CF3COOAg gave a new copper(II) salt – Cu(CF3COO)NO3,20b
which may assist the deprotonation of species B to generate a
more stable complex C. Subsequent ligand exchange of comꢀ
plex C with 1a releases the nitration product 2a, and complex
A is regenerated for recycling.
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3. CONCLUSION
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In conclusion, we have reported the first example of catalytic
meta-selective CArꢀH nitration of a wide range of 2ꢀaryl Nꢀ
.
aromatics using Ru3(CO)12 as the catalyst, Cu(NO3)2 3H2O as
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the nitro source. The generated nitration products represent a
class of super useful intermediates for further transformations
and a shortꢀcut synthesis to a number of pharmaceutical interꢀ
mediates, clinical candidates, as well as marketed drugs. Furꢀ
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talized and confirmed as the active catalyst.
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10.1002/anie.201600490.
ASSOCIATED CONTENT
Supporting Information.
1
Experimental procedures, characterization data, and H and 13C
NMR spectra for all new compounds, and Xꢀray for complex A
(CCDC 1456692). This material is available free of charge via the
(12) (a) Phipps, R. J.; Gaunt, M. J. Science 2009, 323, 1593. (b) Duong, H.
A.; Gilligan, R. E.; Cooke, M. L.; Phipps, R. J.; Gaunt, M. J. Angew.
Chem., Int. Ed. 2011, 50, 463.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: aozhang@simm.ac.cn
(13) (a) Saidi, O.; Marafie, J.; Ledger, A. E.; Liu, P. M.; Mahon, M. F.;
KociokꢀKohn, G.; Whittlesey, M. K.; Frost, C. G. J. Am. Chem. Soc. 2011,
133, 19298. (b) Paterson, A. J.; JohnꢀCampbell, S. S.; Mahon, M. F.;
Pressc, N. J.; Frost, C. G. Chem. Commun. 2015, 51, 12807.
Notes
The authors declare no competing financial interest.
(14) (a) Ackermann, L.; Hofmann, N.; Vicente, R. Org. Lett. 2011, 13,
1875. (b) Hofmann, N.; Ackermann, L. J. Am. Chem. Soc. 2013, 135,
5877. (c) Li, J.; Warratz, S.; Zell, D.; De Sarkar, S.; Ishikawa, E. E.;
Ackermann, L. J. Am. Chem. Soc. 2015, 137, 13894.
ACKNOWLEDGMENTS
T
his work was supported by grants from Chinese NSF
(81430080, 81373277), and the Major State Basic Research
Development Program (2015CB910603). Part of the work was
(15) Teskey, C. J.; Lui, A. Y. W.; Greaney, M. F. Angew. Chem., Int. Ed.
2015, 54, 11677.
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