ORGANIC
LETTERS
2012
Vol. 14, No. 1
354–357
Palladium-Catalyzed
Direct ortho-Alkynylation of
Aromatic Carboxylic Acid Derivatives
Yusuke Ano,† Mamoru Tobisu,*,‡ and Naoto Chatani*,†
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita,
Osaka 565-0871, Japan, and Center for Atomic and Molecular Technologies, Graduate
School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
tobisu@chem.eng.osaka-u.ac.jp; chatani@chem.eng.osaka-u.ac.jp
Received November 19, 2011
ABSTRACT
The palladium-catalyzed direct alkynylation of CÀH bonds in aromatic carboxylic acid derivatives is described. The use of 8-aminoquinoline as a
directing group facilitates the alkynylation of an electronically diverse range of C(sp2)ÀH bonds.
Alkynes are ubiquitous targets in many aspects of
organic chemistry, for example, as synthetic intermediates1
or unique linear structural motifs.2 The development of
effective methods for the incorporation of this functional
group is an important area of research. Although the
SonogashiraÀHagihara reaction3 is the traditional meth-
od of choice, the direct alkynylation of CÀH bonds has
recently emerged as a straightforward alternative, espe-
cially for the construction of C(sp2)ÀC(sp) bonds.4,5 To
date, the direct alkynylation of a wide range of heteroar-
enes, such as azoles and thiophenes, have been reported.6
In contrast, the direct alkynylation of benzene derivatives
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† Department of Applied Chemistry, Faculty of Engineering.
‡ Center for Atomic and Molecular Technologies, Graduate School of
Engineering.
(1) Diederich, F., Stang, P. J., Tykwinski, R. R., Eds. Acetylene
Chemistry; Wiley-VCH: Weinheim, 2005.
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r
10.1021/ol203100u
Published on Web 12/07/2011
2011 American Chemical Society