4318 Organometallics, Vol. 23, No. 18, 2004
Nishikata et al.
basicity of [M]-OR complexes,7 transmetalation takes
place without any assistance of bases for Pd,3 Rh,8 and
Re9 complexes. Thus, cross-coupling reactions of these
compounds often proceed under neutral conditions for
organic electrophiles, directly yielding RO-Pd com-
plexes via oxidative addition. Indeed, the cross-coupling
reactions of boron or silicon compounds with allylic
acetates,10 allylic carbonates,11 1,3-butadiene monox-
ide,12 propargyl carbonates,13 acetic anhydrides,14 and
phenyl trifluoroacetate15 have been carried out in the
absence of bases. Such (alkoxo)palladium(II) complexes
are also considered to be an intermediate of cross-
coupling reactions of organoboron compounds in basic
media, since they are obtained in situ by ligand ex-
change between R-Pd-X and a base.16 The third
process is transmetalation to cationic transition-metal
complexes (eq 3). Cross-coupling reactions of boron and
magnesium reagents have been achieved by a catalytic
cycle starting from transmetalation to yield an aryl- or
1-alkenylrhodium(I) intermediate. The corresponding
addition reactions catalyzed by palladium complexes are
rare; however, there are some reports that palladium-
(II) complexes catalyze 1,4-addition to enones. The Heck
reaction of aryl halides with enones often predominated
the formation of Michael-type products over alkene
products derived by an insertion-elimination process.25
The 1,4-addition of ArHgCl,26 SnAr4,26 ArB(OH)2,27 and
ArSi(OMe)328 to enones was carried out by using neutral
palladium(II) catalysts in acidic media in the presence
of Bu4NCl or a Lewis acid such as SbCl3. We have
recently reported that arylboronic acids easily trans-
metalate to [Pd(dppe)]2+, in which 1,4-addition to enones
was carried out in an aqueous medium at room tem-
perature for arylboronic acids29 and at 75 °C for aryl-
siloxanes30 (Scheme 1). These reactions take place under
neutral conditions by a process analogous to that shown
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silicon compounds with Ph2IBF417 and ArN2BF4,18 which
afford an Ar-[Pd]+ intermediate via oxidative addition,
have been carried out in the absence of bases. Another
example reported in this category is a stoichiometric
reaction between [Pt(S)2(PEt3)2][CF3SO3]2 (S ) MeOH,
H2O) and [Ph4B]Na, Ph3B, or PhB(OH)2, giving [Pt(Ph)-
(S)(PEt3)2]2+ 19
.
Such transmetalation of B, Si, and Sn compounds to
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demonstrated in their addition reactions to alkenes and
alkynes.1 Rhodium(I) complexes were found to be excel-
lent catalysts for 1,4-addition of aryl- or-1-alkenylbo-
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R,â-unsaturated carbonyl compounds and to other ac-
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bonds or triple bonds.24 Various addition reactions
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