ORGANIC
LETTERS
2009
Vol. 11, No. 7
1607-1610
Direct Amination of Azoles via Catalytic
C-H, N-H Coupling
Daiki Monguchi, Taiki Fujiwara, Hirotoshi Furukawa, and Atsunori Mori*
Department of Chemical Science and Engineering, Kobe UniVersity, 1-1 Rokkodai,
Nada, Kobe 657-8501, Japan
Received February 11, 2009
ABSTRACT
C-H, N-H Coupling of azoles takes place with several amines in the presence of a copper catalyst to undergo amination at the 2-position.
The reaction of benzothiazole with N-methylaniline in the presence of sodium acetate and 20 mol % Cu(OAc)2 in xylene under an oxygen
atmosphere afforded the aminated product in 81% yield.
Transition-metal-catalyzed C-H functionalization reactions
are of great interest in organic synthesis because the reaction
shows an advantage in atom efficiency compared to related
cross-coupling with organometallic compounds.1 The reac-
tion of heteroaromatic compounds is particularly important
because of their wide utilities in the synthesis of biologically
active molecules and advanced organic materials.2 The
catalytic carbon-carbon bond-forming reaction via C-H
functionalization has been achieved by the reaction of aryl
halides3,4 or simple arenes at the carbon-hydrogen bond.5
(Buchwald-Hartwig reactions)6 and organometallic com-
pounds (oxidative coupling)7 have been developed so far.
In contrast, limited examples are shown for intra-8 and
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(b) Kobayashi, K.; Sugie, A.; Takahashi, M.; Masui, K.; Mori, A. Org.
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In addition to such carbon-carbon bond-forming reactions,
carbon-heteroatom bond formation is also an important
issue, and a variety of reactions with organic halides
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10.1021/ol900298e CCC: $40.75
Published on Web 03/02/2009
2009 American Chemical Society