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Communication
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Scheme 4. Regioselective Cyanation of Arene C−H Bonds
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example of how our approach can readily be utilized for the
generation of isomeric benzonitriles upon the choice of cyanation
routes.
In conclusion, we have developed a new procedure of the
copper-mediated cyanation using ammonium iodide and DMF.
Boronic acids, boronate esters, borate salts, and electron-rich
arenes were efficiently cyanated with broad substrate scope and
high functional group tolerance. The reaction was proposed to
proceed in two steps via initial iodination and subsequent
cyanation. Ammonium iodide plays a dual role to supply iodide
and nitrogen atom of the cyano unit, thus representing the first
example of utilizing both cationic and anionic species of
ammonium salts in metal-mediated reactions. Further studies
on the details of the cyanide-generating process are underway.
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(21) It is postulated that the partial olefin isomerization occurs
duringthe Cu-mediated oxidative addition of in situ formedβ-iodostyrene:
Li, L.-H.; Pan, Z.-L.; Duan, X.-H.; Liang, Y.-M. Synlett 2006, 2094.
(22) Boronic Acids: Preparation and Applications in Organic Synthesis
and Medicine; Hall, D. G., Eds.; Wiley-VCH: Weinheim, 2005.
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ASSOCIATED CONTENT
■
S
* Supporting Information
Detailed experimental procedure and characterization of new
compounds, including 1H and 13C NMR spectra. This material
AUTHOR INFORMATION
■
Corresponding Author
Notes
(24) See the Supporting Information for more details.
(25) X-Ray powder diffraction spectra of the precipitate and CuI as a
reference were compared (see the Supporting Information).
(26) (a) Li, C.-J. Acc. Chem. Res. 2009, 42, 335. (b) Shirakawa, E.;
Uchiyama, N.; Hayashi, T. J. Org. Chem. 2011, 76, 25.
(27) Chiba, S.; Zhang, L.; Lee, J.-Y. J. Am. Chem. Soc. 2010, 132,
7266.
(28) Iodine generation was confirmed by starch indicator (see the
Supporting Information). For related references, see: (a) Lyday, P. A. In
Ullmann’s Encyclopedia of Industrial Chemistry, 5th Completely Revised
ed.; VCH: Weinheim, 1991; Vol. A14, pp 388−389. (b) Mohan, K. V. V.
K.; Narender, N.; Kulkarni, S. J. Tetrahedron Lett. 2004, 45, 8015.
(29) The use of acetic acid alone in the absence of DMF did not
provide nitrile products. Thus, a possibility of delivering the carbon
source by acetic acid might be ruled out.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by the Korea Research Foundation
Grant (KRF-2008-C00024, Star Faculty Program) and MIRC
(NRF-2011-0001322).
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