A R T I C L E S
Hatakeyama et al.
Scheme 1. Transition Metal-Catalyzed Biaryl Coupling Reaction
since the seminal work of Kharasch and co-workers who
discovered that aryl Grignard reagents undergo efficient
homocoupling in the presence of catalytic amounts of first-
row transition metal salts, such as the chloride salts of
chromium, manganese, iron, cobalt, nickel, and copper.4
Indeed, recent progress in this oxidative coupling chemistry
has extended their utility to the synthesis of various func-
tionalized biaryls.5 The advancement of both reductive and
oxidative biaryl coupling reactions notwithstanding, transition
metal-catalyzed cross-coupling reactions are the popular
choice, holding the synthetic advantages such as high
selectivity, broad substrate scopes, and mild reaction condi-
tions.6 In fact, a wide range of arylmetal compounds has been
successfully utilized to date as the nucleophilic partner in
unsymmetrical biaryl coupling reactions (Scheme 1). While
one may use aryllithium,7 magnesium,8 boron,9 silicon,10
copper,11 zinc,12 or tin compounds,13 arylmagnesium com-
pounds seem ideal for practical synthesis because they are
readily available, cheap and environmentally benign. Despite
these synthetic advantages of arylmagnesium compounds,
there is one serious drawback associated with their use: the
considerable generation of the symmetrical biaryls via
undesired homocouplings of the arylmagnesium compound
and/or the aryl electrophile. This issue often hampers their
general application for industrial production of biaryls.
We have been interested in the development of iron-
catalyzed reactions,14-16 and launched a thorough investiga-
tion of iron catalysis to overcome the above-mentioned
synthetic problem associated with the unwanted homocou-
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