Journal of the American Chemical Society
Communication
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benzofuran, pyrole, indole, and pyridine proceeds smoothly to
give the corresponding amidation products in moderate to good
yields (7a−7i). Unfortunately, thiophene-based substrates
decompose under these conditions. Considering the frequent
presence of multiple heterocycles within drug molecules, we
tested the coupling of heteroarenes with heteroanilines. Again,
amination of heteroarenes such as furan, benzofuran, pyrole,
pyrazole, and imidazole gave the desired products in moderate to
good yields (7j−7n) except for a single example (7o), making
this method broadly useful for synthesis of a family of biologically
active 2-benzamidobenzoic acids and N-phenylaminobenzo-
ates.12−14 Interestingly, amination of pyridine substrate 1ae
occurs predominantly at the 4-position to give 7p selectively in
36% yield. In most cases, the remaining heterocyclic starting
materials decomposed. Removal of this amide−oxazoline DG
was demonstrated by treating product 3a2 with 2 N KOH/EtOH
at 80 °C to release the corresponding carboxylic acid and
oxazolyamide DG in good yields (Scheme 1).
(3) (a) Stoichiometric hydroxylation of N-benzoyl-2-methylalanine
using Cu(0)/trimethylamine N-oxide: Reinaud, O.; Capdevielle, P.;
Maumy, M. J. Chem. Soc., Chem. Commun. 1990, 566. (b) Stoichiometric
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In summary, we have developed a copper(II)-mediated C−H
amidation and amination with a variety of sulfonamides, amides,
and anilines. The exceptional compatibility of this amination
with multiple heteroatoms present in both reactants renders this
reaction highly valuable for the synthesis of medicinally
important compounds using readily available benzoic acids.
ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental procedures and spectral data. This material is
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, the CAS/SAFEA International
Partnership Program for Creative Research Teams, and The
Recruitment Program of Global Experts for financial support.
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