ORGANIC
LETTERS
2011
Vol. 13, No. 20
5540–5543
An Efficient and General Method for the
Heck and BuchwaldÀHartwig Coupling
Reactions of Aryl Chlorides
Dong-Hwan Lee, Abu Taher, Shahin Hossain, and Myung-Jong Jin*
Department of Chemical Science and Engineering, Inha University, Incheon 402-751,
South Korea
Received August 22, 2011
ABSTRACT
The β-diketiminatophosphane Pd complex acted as a powerful catalyst for the Heck coupling of aryl chlorides with alkenes. Various aryl and
heteroaryl chlorides were coupled efficiently under relatively mild conditions. Furthermore, this catalytic system also proved to be highly active in
the BuchwaldÀHartwig coupling of deactivated and sterically hindered aryl chlorides at room temperature.
Palladium-catalyzed coupling reactions have remarkably
advanced organic synthesis over the past few decades.1
Among them, the Heck coupling is one of the most valu-
able and familiar methods for the construction of carbonÀ
carbon bonds.2 A variety of palladium catalysts has
been extensively studied for efficient and general Heck
coupling.3 It seems limited to aryl bromides and iodides as
useful coupling substrates. The use of aryl chlorides would
be more attractive for industrial applications because of
their low cost and wide availability. However, deactivated
aryl chlorides are reluctant to undergo catalytic reactions
due to their strong CÀCl bonds. It has been recognized
that palladium complexes derived from sterically bulky
electron-rich phosphines,4 N-heterocyclic carbenes,5 and
carbocyclic carbenes6 facilitate the Heck reaction of aryl
chlorides, a substrate class that had previously been in-
accessible. Despite these significant advances, there are
only a few successful examples in the coupling of deactivated
aryl chlorides.7 However, these methods require harsh
reaction conditions such as high reaction temperatures,
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10.1021/ol202177k
Published on Web 09/26/2011
2011 American Chemical Society