Organic Letters
Letter
isolated complex II might be produced through a water-ligand
exchange of I during our workup process. Meanwhile, AgNO3
is oxidized to a bivalent silver salt in the presence of
De Sarkar, S.; Ackermann, L. Top. Organomet. Chem. 2015, 55, 217.
(e) Sharma, R.; Thakur, K.; Kumar, R.; Kumar, I.; Sharma, U. Catal.
Rev.: Sci. Eng. 2015, 57, 345. (f) Yang, J. Org. Biomol. Chem. 2015, 13,
1930. (g) Dey, A.; Agasti, S.; Maiti, D. Org. Biomol. Chem. 2016, 14,
5440.
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4
PhI(TFA) , and a nitrogen dioxide radical (•NO ) is
2
2
1
5
released to attack the para position of the C−Ru bond,
affording Ru(II) species III. Subsequently, the reductive
(
3) (a) Saidi, O.; Marafie, J.; Ledger, A. E.; Liu, P. M.; Mahon, M. F.;
Kociok-Kohn, G.; Whittlesey, M. K.; Frost, C. G. J. Am. Chem. Soc.
011, 133, 19298. (b) Marce, P.; Paterson, A. J.; Mahon, M. F.; Frost,
7
deprotonation of III delivers intermediate IV. Finally, ligand
2
́
exchange of IV with CF COOH releases the meta-nitrated
3
C. G. Catal. Sci. Technol. 2016, 6, 7068.
product 2a and regenerates the active Ru(II) catalyst for the
next catalytic cycle.
(4) (a) Hofmann, N.; Ackermann, L. J. Am. Chem. Soc. 2013, 135,
5877. (b) Li, J.; Warratz, S.; Zell, D.; De Sarkar, S.; Ishikawa, E. E.;
Ackermann, L. J. Am. Chem. Soc. 2015, 137, 13894. (c) Paterson, A. J.;
St. John-Campbell, S.; Mahon, M. F.; Press, N. J.; Frost, C. G. Chem.
Commun. 2015, 51, 12807. (d) Li, G.; Ma, X.; Jia, C.; Han, Q.; Wang,
Y.; Wang, J.; Yu, L.; Yang, S. Chem. Commun. 2017, 53, 1261.
In summary, a versatile, removable oxime-mediated meta-C−
H nitration of arenes has been developed. Dioxygen as
cooxidant is crucial for achieving high conversion and yields.
Mechanistic investigations and DFT calculations have revealed
that an octahedral cycloruthenated complex may be responsible
for the radical electrophilic meta-C−H nitration of arenes. A
plethora of functional groups were well-tolerated. In addition to
the easy-cleavage and convenience for further transformations
of the oxime as the DG, the present reaction protocol has been
further applied for the late-stage modification of clinically
prescribed drugs and nucleosides.
(5) (a) Teskey, C. J.; Lui, A. Y.; Greaney, M. F. Angew. Chem., Int. Ed.
2
015, 54, 11677. (b) Yu, Q.; Hu, L.; Wang, Y.; Zheng, S.; Huang, J.
Angew. Chem., Int. Ed. 2015, 54, 15284. (c) Warratz, S.; Burns, D. J.;
Zhu, C.; Korvorapun, K.; Rogge, T.; Scholz, J.; Jooss, C.; Gelman, D.;
Ackermann, L. Angew. Chem., Int. Ed. 2017, 56, 1557.
(6) (a) Ruan, Z.; Zhang, S.-K.; Zhu, C.; Ruth, P. N.; Stalke, D.;
Ackermann, L. Angew. Chem., Int. Ed. 2017, 56, 2045. (b) Li, Z.-Y.; Li,
L.; Li, Q.-L.; Jing, K.; Xu, H.; Wang, G.-W. Chem. - Eur. J. 2017, 23,
3
285.
(
(
(
7) Fan, Z.; Ni, J.; Zhang, A. J. Am. Chem. Soc. 2016, 138, 8470.
8) For detailed information, see the Supporting Information.
9) Liang, Y.-F.; Wang, X.; Yuan, Y.; Liang, Y.; Li, X.; Jiao, N. ACS
ASSOCIATED CONTENT
Supporting Information
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*
S
Catal. 2015, 5, 6148.
(10) For selected examples of ortho-C−H activation of Diazepam,
see: (a) Khan, R.; Felix, R.; Kemmitt, P. D.; Coles, S. J.; Day, I. J.;
Tizzard, G. J.; Spencer, J. Adv. Synth. Catal. 2016, 358, 98. (b) Min,
M.; Kang, D.; Jung, S.; Hong, S. Adv. Synth. Catal. 2016, 358, 1296.
1
Experimental procedures, characterization data and H
and 13C NMR spectra for all new compounds (PDF)
(c) Shu, S.; Fan, Z.; Yao, Q.; Zhang, A. J. Org. Chem. 2016, 81, 5263.
Crystallographic data for II (CCDC 1534973) (CIF)
(11) Simmons, E. M.; Hartwig, J. F. Angew. Chem., Int. Ed. 2012, 51,
3
(
066.
12) Calculation was performed with Gaussian 09, revision D.01,
based on the crystal structure of intermediate II at the level of B3LYP/
AUTHOR INFORMATION
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-31g*(H, C, N, O, F) and LANL2DZ (Ru).
*
(13) For selected examples of predicting the regioselectivity of
electrophilic aromatic substitution, see: (a) Hirao, H.; Ohwada, T. J.
Phys. Chem. A 2003, 107, 2875. (b) Kruszyk, M.; Jessing, M.;
Kristensen, J. L.; Jorgensen, M. J. Org. Chem. 2016, 81, 5128.
c) Hisamatsu, Y.; Kumar, S.; Aoki, S. Inorg. Chem. 2017, 56, 886.
d) Tamura, Y.; Hisamatsu, Y.; Kumar, S.; Itoh, T.; Sato, K.; Kuroda,
ORCID
Notes
(
(
The authors declare no competing financial interest.
R.; Aoki, S. Inorg. Chem. 2017, 56, 812.
14) (a) Liu, Y.-K.; Lou, S.-J.; Xu, D.-Q.; Xu, Z.-Y. Chem. - Eur. J.
010, 16, 13590. (b) Pawar, G. G.; Brahmanandan, A.; Kapur, M. Org.
Lett. 2016, 18, 448.
15) (a) Sabbasani, V. S.; Lee, D. Org. Lett. 2013, 15, 3954. (b) Sun,
(
2
ACKNOWLEDGMENTS
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This work was supported by grants from Chinese NSF
(
(81373277, 81430080). Support from the National Program
J.; Qiu, J.-K.; Wu, Y.-N.; Hao, W.-J.; Guo, C.; Li, G.; Tu, S.-J.; Jiang, B.
Org. Lett. 2017, 19, 754.
on Key Basic Research Project of China (2015CB910603), the
International Cooperative Program (GJHZ1622) and Key
Program of the Frontier Science (160621) of the Chinese
Academy of Sciences, the Shanghai Commission of Science and
Technology (16XD1404600, 14431905300, 14431900400), as
well as grant from CAS Key Laboratory of Receptor Research
of SIMM (SIMM1606YKF-08, SIMM1606YZZ-06) are also
highly appreciated.
REFERENCES
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(
1) For selected recent reviews on remote C−H activation, see:
a) Schranck, J.; Tlili, A.; Beller, M. Angew. Chem., Int. Ed. 2014, 53,
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Angew. Chem., Int. Ed. 2016, 55, 10558.
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Org. Lett. XXXX, XXX, XXX−XXX