Organic Letters
Letter
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deinsertion of norbornene via β-carbon elimination. F can be
trapped by a cyanide ion through ipso-functionalization to
produce 3 with regeneration of Pd(0) catalyst to start the next
cycle. For ortho-free iodoarenes, diaminated intermediate I can
be generated from E through subsequent C−H activation of a
second ortho-position, oxidative addition of N-benzoyloxyamine
of intermediate G, and reductive elimination of H. I undergoes
deinsertion of norbornene via β-carbon elimination and is
trapped by cyanide ion to produce 4.
In conclusion, we developed an efficient protocol for tandem
ortho-C−H-amination and ipso-cyanation of iodoarenes under
norbornene-mediated Pd-catalyzed process, leading to the
synthesis of a series of functionalized 2-aminobenzonitriles that
have potential in the pharmaceutical industry. This reaction was
also used for substitution of two cyano- and four amino-
functionalities in an arene unit under specified conditions. To the
best of our knowledge, we are not aware of any report of such
observation in similar reactions. The other notable features of
this procedure are tolerance to a wide spectrum of functional
groups, relatively mild conditions, applicability to heteroarenes,
and reproduction in gram scale. We believe this will find wide
applications in organic synthesis and in the pharmaceutical
industry.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
1
Experimental procedure, characterization data, and H,
13C NMR and 19F spectra (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
We acknowledge financial support from DST, New Delhi,
through an award of JCB Fellowship to B.C.R. (Grant No. SR/
S2/JCB-11/2008). B.C.R. also thanks the Indian National
Science Academy, New Delhi, for the offer of INSA Senior
Scientist. B.M. thanks CSIR for his fellowship.
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