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Further studies are clearly needed to fully uncover the precise
mechanism of our copper-catalyzed C−H imidation as well as the
significance of the ligand effect in copper catalysis. Nevertheless,
with a direct method for activating/converting otherwise difficult
aromatic substrates in hand, we and others are now in a position
to synthesize a range of new functional arylamine materials.13
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ASSOCIATED CONTENT
■
S
* Supporting Information
Detailed experimental procedures and spectral data for all
compounds, including scanned images of H and 13C NMR
1
spectra. This material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
(8) Reports on intermolecular C−H amination with 1 equiv of arenes:
(a) Boursalian, G. B.; Ngai, M.-Y.; Hojczyk, K. N.; Ritter, T. J. Am. Chem.
Soc. 2013, 135, 13278. (b) Foo, K.; Sella, E.; Thome, I.; Eastgate, M. D.;
Baran, P. S. J. Am. Chem. Soc. 2014, 136, 5279.
ACKNOWLEDGMENTS
■
This work was supported by the ERATO program from JST
(K.I.) and a Grant-in-Aid from JSPS (26888007 to K.M.). We
thank Dr. Yasutomo Segawa and Mr. Takehisa Maekawa for
assistance with X-ray crystallography, Dr. Keiko Kuwata with
HRMS measurement, and Mr. Kei Muto with KIE experiments.
Mr. Kyohei Ozaki is acknowledged for preparation of the starting
materials. We thank Dr. Ayako Miyazaki and Prof. Cathleen M.
Crudden for critical comments, and Prof. Jay Siegel for the
generous gift of corannulene. ITbM is supported by the World
Premier International Research Center (WPI) Initiative, Japan.
(9) Reviews on C−H activation in the synthesis of bioactive
compounds and organic materials: (a) Yamaguchi, J.; Yamaguchi, A.
D.; Itami, K. Angew. Chem., Int. Ed. 2012, 51, 8960. (b) Wencel-Delord,
J.; Glorius, F. Nat. Chem. 2013, 5, 369. (c) Segawa, Y.; Maekawa, T.;
Itami, K. Angew. Chem., Int. Ed. 2015, 54, 66.
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III; Warren, T. H. Organometallics 2012, 31, 7728. (b) Zheng, C.; You,
S.-L. RSC Adv. 2014, 4, 6173. (c) Zhang, H.; Song, Y.; Zhao, J.; Zhang, J.;
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