Rh-catalyzed addition of boronic acids to alkynes for the synthesis of trisubstituted alkenes in a biphasic system - Mechanistic study and recycling of the Rh/m-TPPTC catalyst

Article abstract of DOI:10.1016/j.jorganchem.2004.07.025

The versatile preparation of trisubstituted alkenes via selective Rh-catalyzed arylation of alkynes is described in water and in a water/toluene biphasic system. For hydrophobic alkyl alkynes, the reaction afforded either alkenes or dienes depending on the temperature and the solvent conditions. Aryl, heteroaryl, silylated and alkyl substituted alkynes reacted equally well with various boronic acids, leading regioselectively to functionalized alkenyl derivatives in high yields (65-99%). The mechanism was investigated in toluene/water mixture or water and involves a vinylrhodium complex. The efficient recycling of the Rh/m-TPPTC system is disclosed with excellent yield (92-96%) and purity of the alkene.

Full text of DOI:10.1016/j.jorganchem.2004.07.025

Journal of Organometallic Chemistry 689 (2004) 3820–3830
www.elsevier.com/locate/jorganchem
Rh-catalyzed addition of boronic acids to alkynes for the synthesis of
trisubstituted alkenes in a biphasic system - Mechanistic study
and recycling of the Rh/m-TPPTC catalyst
*
*
Emilie Genin, V e´ ronique Michelet , Jean-Pierre Gen eˆ t
Laboratoire de Synth e` se Organique, E.N.S.C.P., UMR7573 11 rue P. e t M. Curie, F-75231 Paris Cedex 05, France
Received 2 April 2004; accepted 16 July 2004
Available online 19 August 2004
Abstract
The versatile preparation of trisubstituted alkenes via selective Rh-catalyzed arylation of alkynes is described in water and in a
water/toluene biphasic system. For hydrophobic alkyl alkynes, the reaction afforded either alkenes or dienes depending on the tem-
perature and the solvent conditions. Aryl, heteroaryl, silylated and alkyl substituted alkynes reacted equally well with various boro-
nic acids, leading regioselectively to functionalized alkenyl derivatives in high yields (65–99%). The mechanism was investigated in
toluene/water mixture or water and involves a vinylrhodium complex. The efficient recycling of the Rh/m-TPPTC system is disclosed
with excellent yield (92–96%) and purity of the alkene.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Water-soluble ligand; Boronic acids; Homogeneous biphasic catalysis; Rhodium; Arylation of alkynes
1
. Introduction
alyzed reactions (Scheme 1) [5,6]. Some other modified
triphenylphosphanes such as TPPDS, GUAPHOS have
also been found to be efficient for various C–C bond
formations [4,7].
The transition metal-catalyzed reactions and specifi-
cally homogeneous catalysis have given a considerable
impetus to the progress of the area of organometallic,
organic and industrial chemistries [1]. Among them, car-
bon–carbon bond formations using water-soluble
organometallic catalysts are fundamentally important
because they provide successful solutions to environ-
mental, economic concerns and to the easy product/cat-
alyst separation [2]. Recent years therefore witnessed
tremendous growth in the synthesis of water-soluble lig-
ands to solubilize easily the catalyst precursor in water
We have been engaged for a long time in a program
devoted to reactions in organoaqueous media using
TPPTS ligand [4,8], such as palladium-catalyzed reac-
tions [8,9], nickel-catalyzed cross-couplings [10], palla-
dium, rhodium or nickel-catalyzed ene-reaction [11]
and palladium and platinum-catalyzed carboalkoxycyc-
lization [12]. Recently, we have reported the versatile
preparation of the water-soluble ligand m-TPPTC
(Scheme 1) [4,13]. The preparation involved a phos-
phorylation starting from 1,3-dibromobenzene followed
by an halogen–lithium exchange and a carboxylation
[3]. The most popular sulfonated ligand TPPTS [4] has
been widely utilized in a variety of transition metal-cat-
with CO (Scheme 2). We have shown that, this ligand
2
was particularly efficient for selected Pd-catalyzed reac-
tions [13,14].
We also investigated Rh-catalyzed addition of boro-
nic acids to unsaturated compounds such as a,b-unsatu-
*
Corresponding authors. Tel.: +33 1 44 27 67 42; fax: +33 1 44 07
1
0 62.
E-mail addresses: michelet@ext.jussieu.fr (V. Michelet), genet
ext.jussieu.fr (J.-P. Gen eˆ t).
@
0
022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.025

E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
3821
ClH N
including the mechanism insights and the recycling of
the catalyst.
2
LiO2C
NaO3S
NH
Me N
2
P
P
P
3
3
3
2. Results and discussion
m-TPPTC
TPPTS
GUAPHOS
2.1. Optimization of the catalyst system
KO S
PPh KO PS
P
N
3
3
2
2
The addition of phenylboronic acid to oct-4-yne 1
was chosen as a standard reaction for the optimization
of the catalytic system (Table 1). Preliminary conditions
used 3 mol% rhodium, 6 mol% of the ligand m-TPPTC
and 5 equiv. of boronic acid at 100 °C in water. Having
in hand a highly water-soluble ligand (1100 g/L), we
decided to conduct the reaction directly in water without
TPPDS
Scheme 1.
Br
LiO C
2
2
steps
I
any surfactant [19]. We screened several Rh precursors
and found that the dimer [Rh(cod)OH] [20] was the
best catalyst to enable the reaction in 99% yield (entry
Br
P
2
3
8
0%
m-TPPTC
1). The alkene 2a was isolated in the presence of the
diene 3a, whose structure and stereochemistry was
1
unambiguously determined by H NMR and NOESY
Scheme 2.
effect [21]. In contrast to Ni [22] or Ti [23] mediated for-
mation of dienes, this reactivity was unprecedented in
the Rh-catalyzed arylation of substituted alkynes. The
formation of 3a, in relation with the Rh-catalyzed
polymerization of phenylacetylene [24], will be discussed
in Section 2.3. We then studied the influence of various
parameters (base, temperature, alkyne/phenylboronic
acid ratio). The potential of a base was previously found
to be of some importance for the Rh-catalyzed additions
of boronic acids [15,11,19,25]. The use of mineral or or-
ganic bases such as Na CO or Et N led to a lower selec-
rated ketones, aromatic and heteroaromatic olefins
Scheme 3) [15]. The arylation of pyridyl-substituted
alkenes and enones afforded the pyridyl derivatives
and the ketones via addition-hydrolysis reaction and
(
1
,4-addition respectively (Eqs. (1) and (2)). This latter
reaction was also developed in asymmetric version using
a chiral cationic BINAP-derivative ligand in ethylene
glycol [16]. The styrene reacted differently and led to
the Heck-compound (Eq. (3)). We sought to evaluate
the reactivity of the new carboxylated ligand for other
C–C bond formations and turned our attention to the
Rh-catalyzed addition of boronic acids to alkynes de-
scribed recently by HayashiÕs group in a dioxane/water
mixture (Eq. (4)) [17]. We found that the use of a Rh/
m-TPPTC system enables the formation of alkenes [18]
and wish to report a full description of our results
2
3
3
tivity (entries 2 and 3). The temperature highly
influenced the outcome of the reaction (entries 4–6).
The formation of 3a was indeed favored at room tem-
perature despite a low yield and longer reaction time
(entry 4). Further improvements were attempted to
completely reverse the selectivity towards the diene (en-
tries 5–7), the highest ratio being 87% so far (entry 7).
Anticipating that the formation of diene might be due
to hydrophobic effects, we conducted the reaction in a
biphasic 1/1 water/toluene phase and were pleased to
find that the desired alkene could be isolated in 99%
yield and 100% selectivity (entry 8). For economic con-
cerns and to avoid boron residues, we then wished to
find out if we could reduce the high number of equiva-
lents of boronic acid. The arylation was still very effi-
cient with 2.5 equiv. of phenylboronic acid (entry 9).
The use of 1.2 equiv. led to still acceptable yield but
the formation of the diene 3a became competitive (entry
10). Lowering the temperature to 50 °C (entry 11) af-
forded a good 84% yield and a selectivity of 95% in fa-
vor of the alkene 2a. At room temperature (entry 12), 5
equiv. of phenylboronic acid were necessary to obtain a
decent yield. Thus, we further pursue our study under
the following optimized conditions: 1.5 mol% of
N
Ar
N
[Rh] / m-TPPTC
Eq 1
Eq 2
ArB(OH)2 / H O
2
O
[
Rh] / m-TPPTC
O
or (R)-DigmBINAP
ArB(OH)2 /H O
*
2
Ar
or HO(CH ) OH
2
2
[
Rh] / m-TPPTC
Ar
Eq 3
Eq 4
ArB(OH) / H O
2
2
Ar
H
[Rh] / m-TPPTC
R
R'
ArB(OH) / H O
2
2
R
R'
Scheme 3.

3822
E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
Table 1
Rh-catalyzed arylation of oct-4-yne
C3H7
[
Rh(cod)OH]2 (1.5%)
m-TPPTC (6%)
Ph
H
Ph
C3H7
C H
C H
C H
3 7
+
3
7
PhB(OH)2, T, t
C3H7
C3H7 C H7
3
3 7
1
2a
3a
a
Yield (%)
b
Entry
Conditions
PhB(OH)
2
(equiv.)
T (°C)
t (h)
2a/3a Ratio
1
2
3
4
5
6
7
8
9
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O
O, Na
5
100
100
100
rt
3
3
99
99
99
26
71
99
30
99
90
75
84
45
80/20
60/40
c
3
2
CO
c
5
d
O, Et
O
3
N
5
3
80/20
5
69
67
67
69
3
40/60
75/25
88/12
13/87
100/0
98/2
O
5
30
50
O
5
c
3
O, Na
2
CO
0.2
5
rt
O/toluene 1/1
O/toluene 1/1
O/toluene 1/1
O/toluene 1/1
O/toluene 1/1
100
100
100
50
2.5
1.2
2.5
5
3
1
1
1
0
1
2
3
92/8
95/5
6.3
66
rt
97/3
a
b
c
Isolated yield.
1
Measured by H NMR and GC.
equiv.
Mixture of 2a and its stereoisomer.
2
d
[
Rh(cod)OH] , 6 mol% of m-TPPTC, 2.5 equiv. of boro-
2
We then studied the reactivity of various alkynes
bearing alkyl, aryl or heteroryl groups and especially
unsymmetrical alkynes. On one hand, Hayashi showed
that the presence of an electron withdrawing such as
an ester or a phosphonate group was crucial for a high
regioselectivity in organoaqueous media [17]. On the
other hand, the reaction was only found to be highly
regioselective in water with 2-heteroaryl substituted
alkynes [19]. The presence of a chelating pyridyl group
was advocated to explain this excellent stereo-outcome.
The case of 1-phenylpropyne was a real challenge too, as
no reaction occurred in water [19] and only a mixture of
regioisomers (3:1) was obtained in the dioxane/water
system [17]. All together, we therefore decided to study
the hydroarylation of 1-phenylpropyne, 1-phenyl-
hexyne, 2-(1-hexynyl)pyridine and 4-(1-hexynyl)pyridine
(Table 3) [27]. We were pleased to find that 1-phenyl-
propyne 4 reacted smoothly: the formation of the ex-
pected alkenes 5a–c was observed with high yields
(entries 1–3). Moreover, the regioselectivity was found
to be >95% as no trace of another isomer was detected
by NMR or GC. The addition of the aryl groups occurs
exclusively at the b position of the phenyl group. The
same selectivity was observed for 1-phenylhexyne 6 as
the addition of 4-methoxyphenylboronic acid led to
the corresponding alkene 7 in 80% yield (entry 4). We
also tested the efficiency of the system with a pyridyl
substituted alkyne and an excellent regioselectivity was
also observed. The alkenes 9 were isolated in high yields
(entries 5–7), regardless the substitution of the aromatic
ring of the boronic acid. The regioselectivity observed
for these two alkynes tends to prove that no chelation-
nic acids, 100 °C.
2
.2. Scope and limitations
We next studied the scope of the reaction by subject-
ing oct-4-yne 1 to a series of substituted boronic acids.
The alkyne 1 reacted very smoothly to form the
corresponding alkenes 2b–j, as shown in Table 2. No
traces of dienes could be detected by H NMR or gas
chromatography.
1
The conditions were compatible with electron-donat-
ing and electron-withdrawing groups as exemplified by
the addition of methylphenylboronic acids (entries 1
and 2), methoxyphenylboronic acids (entries 3 and 4),
and trifluoromethylphenylboronic acid (entry 5). The
corresponding alkenes 2b–f were isolated in 80–99%
yield. It has to be pointed out that in the case of the
methoxyphenylboronic acids, no reduction of the boro-
nic acid to anisole was observed, which makes these con-
ditions very attractive compared to previously described
ones [17]. The arylation was still efficient with hindered
boronic acids (entries 2 and 6) and was completely
chemoselective as bromophenylboronic acid could be
added in 99% yield (entry 7). This latter example was
particularly interesting for further organometallic cou-
pling. Similar chemoselectivity was observed in Rh-cat-
alyzed addition of bromo-substituted boron derivatives
[
15,16,25c,26]. The boronic acids bearing an aldehyde
or a sulfur group were also reactive and led to the
corresponding alkenes 2i–j in 48% and 49% yields,
respectively.

E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
3823
Table 2
Reaction of oct-4-yne 1 with various boronic acids
addition of phenylboronic acid to the alkyne 17 indeed
gave exclusively a unique isomer 18a in 94% yield (entry
4
NOESY analyses. Other boronic acids bearing electron-
donating and electron-withdrawing groups also afforded
the corresponding alkenes 18b,c in 73% and 77% iso-
lated yields (entries 5 and 6).
[
Rh(cod)OH] (1.5%)
1
). The structure of this latter was confirmed by H and
2
m-TPPTC (6%)
Ar
H
C H
C H
3 7
3
7
ArB(OH) (2.5 eq.)
2
C H
C3H7
3
7
H O/toluene (1/1)
2
1
2b-j
100˚C, 3h
a
Entry
Ar
Product
Yield (%)
1
2
3
4
5
6
7
8
9
4-MeC
2-MeC
6
H
H
4
2b
2c
2d
2e
2f
97
99
80
93
99
99
99
48
49
6
4
2
.3. Mechanistic investigation
4-MeOC
3-MeOC
6
6
H
4
H
4
4-CF
1-Naphthyl
4-BrC
4-CHOC
3-Thiophene
3
C
6
H
4
The mechanistic study of the addition of boronic
2g
2h
2i
acids to alkynes was studied in biphasic system and in
water. Considering the previous apparently similar re-
ports [17,19], one may either envisage a vinylrhodium
intermediate or an arylrhodium species. Hayashi re-
ported that the vinylrhodium intermediate A rearranges
to an arylrhodium one B [17]. Lautens proposed a che-
lated alkenylrhodium intermediate, based on deutera-
tion on the alkene position and due to the fact that
only 2-pyridyl substituted substrates are reactive [19].
The rhodium-catalyzed chelation-controlled was ex-
cluded in our case, as we have shown that the hydroary-
lations of either 1-phenylpropyne 4, 1-phenylhexyne 6,
2-(1-hexynyl)pyridine 8, 4-(1-hexynyl)pyridine 10 and
2-(1-hexynyl)thiophene 12 were regioselective (Table
3). We therefore, conducted the reactions in a 1/1
D O/toluene mixture and in D O. The reaction of 1 with
6 4
H
6
H
4
2j
a
Isolated yield.
controlled occurs with our system. This was further con-
firmed in the case of the 4-substituted pyridyl alkyne 10.
Once again, the reaction occurred with a total regiose-
lectivity an led to the 3-methoxyphenyl and napthyl
derivatives 11a,b in 68% and 65% yield, respectively (en-
tries 8 and 9). The 2-(1-hexynyl)thiophene 12 had a sim-
ilar behavior towards the addition of the phenylboronic
acid (entry 10) as the alkene 13 was isolated in 88% yield
as a single isomer. One common feature could come out
from these examples. It seems that the regioselectivity is
directed by the phenyl or the heteroaryl group when the
alkyne is substituted by an alkyl group. An alkyl group
does not therefore influence the regioselectivity of the
reaction.
2
2
PhB(OH) in the biphasic D O/toluene mixture led to
2
2
alkene d-2a, which showed 90% deuterium incorpora-
1
tion at the vinylic position by H NMR analysis
(Scheme 5) [29]. The addition of phenylboronic acid to
oct-4-yne in D O afforded a 8/2 mixture of 2a/3a with
a 70% deuterium incorporation for d-2a.
Based on these experiments, a plausible mechanism
could be described on Scheme 5. The reaction first in-
volves a classic transmetallation leading to a [RhL ]–
2
We decided to investigate the influence of a silyl
group compared to an alkyl and a phenyl group (Table
n
4
). Organosilanes have indeed recently been recognized
Ph intermediate, then a complexation of the catalyst to
the alkyne, and the syn addition [30] to the alkyne lead-
ing to the vinylrhodium specie A. At this stage, the equi-
librium between the intermediate A and an arylrhodium
specie B is a minor phenomena implying a low rate con-
stant in our case as the vinylic intermediate is either
trapped by another molecule of alkyne leading to 3a
(path b) or/and hydrolyzed to give 2a (path a). Subse-
quent hydrolysis with water results in the formation of
the desired alkene and regeneration of the catalyst.
The kinetics of the hydrolysis step (path a) and the sec-
ond addition of the alkyne (path b) are presumably
influenced by the nature of the phosphane. Moreover,
the formation of the diene 3a in water may be due to
the unique structure and properties of water compared
to organic solvents. It is now well-known that water
has the highest cohesive energy density, a very large sur-
face tension and a high heat capacity [1–3]. The princi-
pal consequence of these effects is the entropy-driven
to be practical for various couplings [28]. The additions
of various boronic acids to 4-(trimethylsilylethynyl)
bromobenzene 14 proceed efficiently with high chemose-
lectivity (entries 1–3), leading to corresponding alkenes
1
5 in 98% yield. Nevertheless, these alkenyl compounds
were respectively isolated as a 1/1 mixture of inseparable
isomers 15a–b, 15c–d and 15e–f.
The structures of 15a,b were demonstrated by the
desilylation reaction under standard conditions (n-Bu4
NF in THF at 60 °C) to give the 1/1 mixture of gem-
disubstituted (J = 1.1 Hz) and trans-disubstituted
(
J = 16.5 Hz) alkenes 16 in 99% yield (Scheme 4).
It seems therefore that the trimethylsilyl group has
the same effect as the phenyl group and promotes the
addition of the aryl group at the b position, which
may be explained by the electronic effects of silicium.
This trend was further confirmed by testing the reactiv-
ity of a substrate bearing an alkyl group such as 17. The

3824
E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
Table 3
Reaction of unsymmetrical alkynes with various boronic acids
[
Rh(cod)OH] (1.5%)
m-TPPTC (6%)
2
Ar
R
H
ArB(OH)2
R
R'
+
H O/toluene (1:1)
2
R'
2
.5 eq.
100˚C
a
yield (%)
Entry
1
Alkyne
Ar
Product
t (h)
4
4
C
6
H
5
5a
5b
2.5
95
H
C H
6 5
H C
5
6
2
3-MeOC
6
H
4
2.5
96
H
H
H C
OMe
Br
5
6
3
4
4
6
4-BrC
6
H
4
5c
7
2.5
3
73
80
H C
5
6
6 4
4-MeOC H
H
4 9
C H
H C
5
6
OMe
H C
9
4
5
6
8
8
C
6
H
5
9a
9b
3
3
98
98
C H
4
9
N
N
N
N
C H
6
5
C4H9
H
6 4
3-MeOC H
C H
4
9
OMe
C4H9
H
H
7
8
2-Naphtyl
9c
3
80
C H
4
9
N
N
C4H
9
8
9
10
3-MeOC
6
H
4
11a
3
68
N
N
C H
4
9
N
N
C H
4
9
OMe
H
10
12
2-Naphtyl
11b
13
3
3
65
88
C H
4
9
C H
4
9
H
1
0
6 5
C H
C H
4
9
S
C H
S
C6H5
4
9
H
a
Isolated yield.
association of apolar solutes in water. The hydrophobic
effect in our case, due to the low water-solubility of the
alkyl alkyne, may therefore promote a second addition
of alkyne, as several alkynes are close to each other
2.4. Recycling
A major advantage of water-soluble phosphane lies in
the recycling possibility of the catalyst, that is therefore
preserved in water. For that reason we envisaged
improving our catalyst system Rh(I)/m-TPPTC by recy-
cle experiments. We performed the hydroarylation of
oct-4-yne 1 with phenylboronic acid using 1.5 mol%
(
Fig. 1). The use of a biphasic system may control the
concentration [31] of the alkyne in the water phase
and therefore influences the selectivity of the reaction
in favor of the monoaddition of the alkyne.

E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
3825
Table 4
Reaction of unsymmetrical silylated alkynes with various boronic acids
[
Rh(cod)OH]2 (1.5%)
m-TPPTC (6%)
Me
3
Si
H
R
Me
3
Si
R
+
ArB(OH)
.5 eq.
2
H
2
O/toluene (1:1)
00˚C, 3h
Ar
2
1
a
Entry
1
R
Ar
Product
Yield (%)
b
99
4-BrC
6
H
4
14
14
C
6
H
5
SiMe3
SiMe3
15a,b
15c,d
H C
H
5
6
Br
+
Br
H
C H
6
5
b
98
2
3
4-BrC
6
H
4
2-MeC
6
H
4
SiMe3
SiMe3
H
+
Br
Br
H
b
98
4-BrC
6
H
4
14
3-MeOC
6
H
4
MeO
SiMe3
15e,f
SiMe3
H
+
Br
Br
H
OMe
4
5
C
C
4
4
H
9
9
17
17
C
6
H
5
18a
18b
94
73
Me Si
C4H9
C6H5
3
H
H
6 4
4-MeOC H
H C
9
4
OMe
CF3
Me Si
3
H
6
C
4
H
9
17
4-CF
3
C
H
6 4
18c
77
H C
9
4
Me Si
3
H
a
Isolated yield.
1
b
1
/1 Mixture measured by NMR and gas chromatography.
[
Rh(cod)OH] , 6 mol% m-TPPTC under our standard
2
then extracted two times with toluene and reloaded with
substrates. The reaction time was still very short for
each of the 4 cycles (1.5 h). The alkene 2a was isolated
with 93–98% yield and with excellent purity (98%).
conditions. As shown in Fig. 2, we were pleased to find
that the benefits of the water-soluble ligand lied in the
successful recycling of the expensive rhodium. Indeed,
after completion of the reaction, the organic phase (con-
taining the product) was separated, the water phase was
3. Conclusion
SiMe
3
SiMe
3
The rhodium/m-TPPTC system therefore provides a
H
5
C
6
H
Br
+
Br
convenient catalyst for the hydroarylation of substituted
alkynes. The addition of various arylboronic acids to
alkynes afforded very efficiently trisubstituted alkenes
in excellent yields and purity. The reaction was found
to be highly chemo-, stereo- and regioselective in a
water/toluene biphasic system. The conditions were
compatible either with alkyl, aryl, heteroaryl and silyl-
substituted alkynes. The regioselectivity follows a
general trend showing that aromatic and silyl groups
promote the addition of the aryl group at the b position.
H
6
C H
5
15a
15b
n-Bu
4
NF
THF, 60˚C
9
9 %
H
H
H
5 6
H C
Br
+
Br
H
6 5
C H
16a
16b
Scheme 4.

3826
E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
C3H7
(
D)H
Ph
[
Rh(cod)OH] (1.5%)
m-TPPTC (6%)
2
Ph
H(D)
C3H
7
C3H7
C3H7
+
PhB(OH) (5 eq.) C H
C H
3
C H
3 7
C3H7
2
3
7
7
1
00¡C, 3h
1
2a
3a
D O/toluene 1/1 d-2a (90%)
2
D O
2
d-2a (70%)
H O
2
C3H7
C3H7
C3H7
3a
[
LnRh]
Ph
2
a
[
RhL ] OH
n
C H
PhB(OH)2
3
7
H O
2
path a
[RhLn]
B(OH)3
Ph
C H
C H
3
7
3
7
[
RhL ]P
h
n
C H A C H7
3
7
3
Ph
[RhLn]
C H
C3H
3
7
7
path b
C H
C H
3 7
3
7
[
RhLn]
H
[RhL ]P h
n
L= m-TPPTC
C H
3
C H
3 7
7
B
Scheme 5.
efficiently too. Further applications of the rhodium/m-
TPPTC system are currently under high investigation
in our laboratory and will be reported in due course.
4
. Experimental
Reagents were commercially available from Acros,
Aldrich or Avocado and used without further purifica-
tion. [Rh(cod)OH] was prepared according to the re-
2
Fig. 1.
ported procedure [20a]. All manipulations involving
air-sensitive reagents were carried out under argon and
Schlenk techniques for catalytic tests. Water and toluene
were degassed by sparging with argon and/or exposure
to vacuum. Column chromatography was performed
with E. Merck 0.040–0.063 mm Art. 11567 silica gel.
Yield Purity
1
00
8
6
4
2
0
0
0
0
0
1
13
19
H NMR, C NMR and FNMR were recorded on
13
1
a Bruker AV 300 instrument. All signals for H,
C
1
9
and FNMR were expressed as ppm down field from,
respectively, Me Si and CFCl used as an internal stand-
4
3
ard (d) Coupling constants (J) are reported in Hz and re-
fer to apparent peak multiplicities. GC analyses were
performed with a Hewlett–Packard 5890 instrument
equipped with a J&W Scientific DB-1701 capillary col-
umn (15 m, d = 0.254 lm), using flame ionization detec-
tor. Elemental analyses were performed at the
University of Pierre et Marie Curie (UPMC Paris VI).
Mass spectrometry analyses were performed at the Ecole
Nationale Sup e´ rieure de Chimie de Paris with a Hewl-
Cycle 1
Cycle 2
Fig. 2.
Cycle 3
Cycle 4
The mechanism was investigated in water and in tolu-
ene/water biphasic system and involves a vinylrhodium
complex. The recycling of the catalyst was performed

E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
3827
ett–Packard HP 5989 A. Direct introduction experi-
4.1.3. (E)-4-(3-methoxyphenyl)oct-4-ene (2e)
1
ments were done by electronic impact. High resolution
mass spectra were performed on a Varian MAT311
instrument at the Ecole Normale Sup e´ rieure (Paris).
The spectral characterizations of alkenes 2a–b [17], 2d
H NMR (CDCl , 300 MHz): d 0.90 (t, J = 7.3 Hz,
3
3H, CH ), 0.98 (t, J = 7.3 Hz, 3H, CH ), 1.39 (sext,
J = 7.3 Hz, 2H, CH ), 1.49 (sext, J = 7.3 Hz, 2H,
3
3
2
CH ), 2.19 (q, J = 7.3 Hz, 2H, CH ), 2.48 (t, J = 7.3
2
2
[
1
17], 2f [17], 2g [32], 2i [33], 5a [17], 5c [34], 9a [19b],
3 [35], 18a [36] are identical to those published in the
literature.
Hz, 2H, CH ), 3.83 (s, 3H, OCH ), 5.69 (t, J = 7.3 Hz,
2 3
1H, CH), 6.78 (ddd, J = 8.3, 2.6, 0.9 Hz, 1H, CH ar),
6.91 (appt, J = 2.6 Hz, 1H, CH ar), 6.97 (ddd, J = 7.6,
1
.5, 0.9 Hz, 1H, CH ar), 7.23 (appt, J = 7.9 Hz, 1H,
1
3
CH ar); C (CDCl , 75 MHz): d 13.9 (CH ), 14.0
3
3
4.1. Typical procedure for rhodium-catalyzed hydroary-
lation of alkyne with arylboronic acids
(CH ), 21.8 (CH ), 23.1 (CH ), 30.6 (CH ), 31.8
3 2 2 2
(CH ), 55.1 (CH ), 111.5 (CH ar), 112.5 (CH ar),
2 3
119.0 (CH), 129.0 (CH ar), 129.3 (CH ar), 140.0 (Cq
To a degassed mixture of [Rh(cod)OH]2 (1.5
mol%), m-TPPTC (6 mol%) and arylboronic acid
ar), 145.2 (C ), 159.5 (C ar); GC (70 °C, 1 min, 20
q
q
°C/min, 250 °C): t = 8.2 min; MS (EI, m/z): 218
R
+ + +
Å
(
2.5 equiv.) at room temperature was successively
(M) , 189 (MꢀC H ) , 175 (MꢀC H ) . Anal. Calc.
15 22
2
5
3
7
added the alkyne (1 equiv.) and solvents (water/tolu-
ene 1/1, 2.5 M). The mixture was stirred at 100 °C
for 3 h, cooled to room temperature and then filtered
on a short pad of silica gel with 25 mL of ethyl ace-
tate and evaporate under reduce pressure to give the
product. No further purification by silica gel chroma-
tography was necessary.
for C H O: C, 82.52; H, 10.16. Found: C, 82.91; H,
10.58%.
4.1.4. (E)-4-(4-bromophenyl)oct-4-ene (2h)
1
H NMR (CDCl , 300 MHz): d 0.89 (t, J = 7.3 Hz,
3
3H, CH ), 0.98 (t, J = 7.3 Hz, 3H, CH ), 1.36 (sext,
J = 7.3 Hz, 2H, CH ), 1.49 (sext, J = 7.3 Hz, 2H,
3
3
2
CH ), 2.18 (q, J = 7.3 Hz, 2H, CH ), 2.46 (t, J = 7.3
2
2
Hz, 2H, CH ), 5.67 (t, J = 7.3 Hz, 1H, CH), 7.21 (d,
2
4
.1.1. (4Z,6E)-4-phenyl-5,6-dipropyl-4,6-decadiene (3a)
1
J = 8.6 Hz, 2H, CH ar), 7.42 (d, J = 8.6 Hz, 2H, CH
13
H NMR (CDCl , 300 MHz): d 0.57 (t, J = 7.1 Hz,
ar); C (CDCl , 75 MHz): d 13.9 (2 CH ), 21.7 (CH ),
3
3
3
2
3
J = 7.1 Hz, 3H, CH ), 0.86 (t, J = 7.1 Hz, 3H, CH ),
H, CH ), 0.73 (t, J = 7.0 Hz, 3H, CH ), 0.78 (t,
23.0 (CH ), 30.7 (CH ), 31.6 (CH ), 120.1 (C ar),
2 2 2 q
3
3
3
3
128.0 (2 CH ar), 129.8 (CH), 131.2 (2 CH ar), 139.1
(C ar), 142.4 (C ); GC (70 °C, 1 min, 20 °C/min, 250
0
1
.91–0.98 (m, 2H, CH ), 1.17–1.37 (m, 6H, 3 CH ),
2
2
q
q
+
Å
.67 (q, J = 7.2 Hz, 2H, CH ), 1.75 (t, J = 7.9 Hz, 2H,
2
°C): t = 8.5 min; MS (EI, m/z): 266 (M) , 239
R
+ +
+Å
CH ), 2.13 (t, J = 7.9 Hz, 2H, CH ), 2.28 (t, J = 7.5
2
(MꢀC H ) , 223 (MꢀC H ) ; HRMS-EI: (M) . Cal-
14 19
2
2
5
3
7
Hz, 2H, CH ), 4.83 (t, J = 7.2 Hz, 1H, CH), 6.95–7.04
2
culated for C H Br: 266.0670, 268.0651. Found
266.0673, 268.0653.
1
m, 3H, CH ar), 7.08–7.13 (m, 2H, CH ar); C (CDCl3,
3
(
7
5 MHz): d 14.7 (CH ), 15.0 (CH ), 15.1 (CH ), 15.6
3
3
3
(
(
(
CH ), 22.4 (CH ), 22.7 (CH ), 22.9 (CH ), 23.5
CH ), 30.7 (CH ), 33.4 (CH ), 34.4 (CH ), 37.4
4.1.5. (E)-3-(1-propyl-pent-1-enyl)-thiophene (2j)
1
3
2
2
2
2
2
2
2
H NMR (CDCl , 300 MHz): d 0.85 (t, J = 7.5 Hz,
3
CH ), 126.1 (CH), 128.1 (2 CH ar), 130.4 (2 CH ar),
2
3H, CH ), 0.89 (t, J = 7.2 Hz, 3H, CH ), 1.35 (sext,
J = 7.2 Hz, 4H, 2 CH ), 2.08 (q, J = 7.5 Hz, 2H, CH ),
2 2
3
3
1
32.1 (CH ar), 137.1 (C ), 140.1 (C ), 141.9 (C ), 145.5
q
q
q
(
C ); GC (70 °C, 1 min, 20 °C/min, 250 °C): t = 8.9
2.34 (t, J = 7.2 Hz, 2H, CH ), 5.75 (t, J = 7.2 Hz, 1H,
2
q
R
+
Å
+
min; MS (EI, m/z): 298 (M) , 255 (MꢀC H ) .
CH), 7.08 (dd, J = 2.8, 1.4 Hz, 1H, CH ar), 7.19–7.26
1
3
7
3
(
m, 2H, CH ar); C (CDCl , 75 MHz): d 13.9 (CH ),
3 3
4
.1.2. (E)-4-(2-methylphenyl)oct-4-ene (2c)
1
14.2 (CH ), 22.2 (CH ), 23.0 (CH ), 30.4 (CH ), 32.0
3 2 2 2
H NMR (CDCl , 300 MHz): d 0.94 (t, J = 7.3 Hz,
(CH ), 118.6 (CH ar), 125.0 (CH), 125.8 (CH ar),
2
3
3
J = 7.3 Hz, 2H, CH ), 1.52 (sext, J = 7.3 Hz, 2H,
H, CH ), 1.03 (t, J = 7.3 Hz, 3H, CH ), 1.36 (sext,
127.9 (CH ar), 134.6 (C ar), 144.3 (C ); GC (70 °C, 1
3
3
q
q
2
min, 20 °C/min, 250 °C): t = 6.8 min; MS (EI, m/z):
R
+ + +
Å
CH ), 2.22 (q, J = 7.3 Hz, 2H, CH ), 2.33 (s, 3H,
2
194 (M) , 179 (MꢀCH ) , 165 (MꢀC H ) , 151
2
3
2
5
+
CH ), 2.38 (t, J = 7.3 Hz, 2H, CH ), 5.31 (t, J = 7.3
3
(MꢀC H ) .
2
3
7
1
Hz, 1H, CH), 7.1–7.2 (m, 4H, CH ar); C (CDCl , 75
3
3
MHz): d 13.9 (CH ), 14.2 (CH ), 19.9 (CH ), 21.4
4.1.6. (E)-1-phenyl-2-(3-methoxyphenyl)propene (5b)
1
3
3
3
(
CH ), 23.1 (CH ), 30.1 (CH ), 33.9 (CH ), 125.2
2
H NMR (CDCl , 300 MHz): d 2.33 (s, 3H, CH ),
2
2
2
3
3
(
1
CH), 126.3 (CH ar), 129.0 (CH ar), 129.8 (CH ar),
29.9 (CH ar), 135.2 (C ar), 140.6 (C ar), 144.7 (C );
3.89 (s, 3H, OCH ), 6.90 (s, 1H, CH), 7.13–7.44 (m,
3
1
3
q
q
q
9H, Har); C (CDCl , 75 MHz): d 17.6 (CH ), 55.3
3 3
GC (70 °C, 1 min, 20 °C/min, 250 °C): t = 6.7 min;
(OCH ), 112.1 (CH ar), 112.5 (CH ar), 118.7 (CH),
3
R
+
Å
+
MS (EI, m/z): 202 (M) , 187 (MꢀCH ) , 173
126.6 (CH ar), 127.9 (CH ar), 128.3 (2 CH ar), 129.2
(2 CH ar), 129.3 (CH ar), 137.4 (C ), 138.3 (C ar),
3
+
+
(
MꢀC H ) , 159 (MꢀC H ) .
2
5
3
7
q
q

3828
E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
1
45.6 (C ar), 159.7 (C ar); GC (150 °C, 1 min, 20 °C/
°C/min, 250 °C): t = 13.1 min; MS (EI, m/z): 287
+ +
q
q
R
+
Å
+Å
min, 250 °C): t = 6.4 min; MS (EI, m/z): 224 (M) , 209
(M) , 272 (MꢀCH ) , 258 (MꢀC H ) , 244
+Å
3 7
R
3
2
5
+
+
+
(
C H O: C, 85.68; H, 7.19. Found: C, 85.33; H, 7.21%.
MꢀCH ) , 194 (MꢀCH OH) . Anal. Calc. for
(MꢀC H ) ; HRMS-EI: (M) . Calculated for
21 21
3
2
C H N: 287.1674. Found 287.1669.
1
6
16
4
.1.7. (E)-1-phenyl-2-(4-methoxyphenyl)hexene (7)
1
4
(
.1.10. (E)-4-[2-(3-methoxyphenyl)-1-hexenyl]pyridine
11a)
H NMR (CDCl , 300 MHz): d 0.76 (t, J = 7.2 Hz,
3
3
Hz, 2H, CH ), 3.73 (s, 3H, CH ), 6.56 (s, 1H, CH),
H, CH ), 1.17–1.36 (m, 4H, 2 CH ), 2.59 (t, J = 7.2
3
2
1
H NMR (CDCl , 300 MHz): d 0.88 (t, J = 7.2 Hz,
3
2
3
3
J = 7.2 Hz, 2H, CH ), 3.85 (s, 3H, OCH ), 6.58 (s, 1H,
H, CH ), 1.26–1.45 (m, 4H, 2 CH ), 2.68 (appt,
3 2
6
ar), 7.31 (d, J = 8.8 Hz, 2H, CH ar); C (CDCl , 75
.81 (d, J = 8.8 Hz, 2H, CH ar), 7.13–7.26 (m, 5H, CH
1
3
2
3
3
CH), 6.88 (ddd, J = 8.4, 2.5, 0.9 Hz, 1H, CH ar), 6.98
appt, J = 1.6 Hz, 1H, CH ar), 7.03 (ddd, J = 7.8, 1.5,
MHz): d 13.9 (CH ), 22.8 (CH ), 29.9 (CH ), 31.0
3
2
2
(
(
CH ), 55.3 (OCH ), 113.7 (2 CH ar), 126.3 (CH),
2 3
0
7
2
.9 Hz, 1H, CH ar), 7.20 (d, J = 5.8 Hz, 2H, CH ar),
.29 (t, J = 7.9 Hz, 1H, CH ar), 8.58 (d, J = 5.8 Hz,
1
26.8 (CH ar), 127.6 (2 CH ar), 128.1 (2 CH ar), 128.8
(
2 CH ar), 135.5 (C ), 138.6 (C ar), 142.7 (Cq ar),
q q
1
3
H, CH ar); C (CDCl , 75 MHz): d 13.8 (CH ), 22.7
1
58.9 (C ar); GC (70 °C, 1 min, 20 °C/min, 250 °C):
3
3
q
+
Å
+
(CH ), 30.3 (CH ), 30.8 (CH ), 55.3 (OCH ), 112.7
2 2 2 3
t = 11.2 min; MS (EI, m/z): 266 (M) , 209 (MꢀCH ) ,
R
3
+
+Å
(
1
CH ar), 112.9 (CH ar), 119.1 (CH), 123.5 (2 CH ar),
25.4 (CH ar), 129.4 (CH ar), 143.9 (C ar), 145.8 (C
q
1
C H O: 266.1671. Found 266.1672.
94 (MꢀOCH ) ; HRMS-EI: (M) . Calculated for
3
q
19 22
ar), 147.2 (C ), 149.8 (2 CH ar), 159.7 (Cq ar); GC
q
(
130 °C, 1 min, 20 °C/min, 250 °C): t = 9.1 min; MS
R
4
(
.1.8. (E)-2-[2-(3-methoxyphenyl)-1-hexenyl]pyridine
9b)
+Å
+
(
(
EI, m/z): 267 (M) , 224 (MꢀC H ) ; HRMS-EI:
+Å
18 21
3
7
M) . Calculated for C H ON: 267.1623. Found
67.1625.
1
H NMR (CDCl , 300 MHz): d 0.85 (t, J = 7.1 Hz,
3
2
3H, CH ), 1.32–1.45 (m, 4H, 2 CH ), 3.03 (app t,
J = 8.0 Hz, 2H, CH ), 3.84 (s, 3H, CH ), 6.72 (s, 1H,
3
2
2
3
CH), 6.86 (ddd, J = 8.2, 2.6, 0.9 Hz, 1H, CH ar), 7.05
appt, J = 7.7 Hz, 1H, CH ar), 7.09–7.13 (m, 2H, CH
4
.1.11. (E)-4-[2-(2-naphthyl)-1-hexenyl]pyridine (11b)
1
(
H NMR (CDCl , 300 MHz): d 0.86 (t, J = 7.2 Hz,
ar), 7.26–7.32 (m, 2H, CH ar), 7.65 (apptd, J = 7.7, 1.9
Hz, 1H, CH ar), 8.64 (ddd, J = 4.8, 1.7, 0.8 Hz, 1H,
3
3
Hz, 2H, CH ), 6.72 (s, 1H, CH), 7.25 (d, J = 6.0 Hz,
H, CH ), 1.35–1.47 (m, 4H, 2 CH ), 2.82 (t, J = 7.2
3 2
1
3
CH ar); C (CDCl , 75 MHz): d 13.9 (CH ), 22.8
2
3
3
2
J = 8.7, 1.9 Hz, 1H, CH ar), 7.84–7.91 (m, 4H, CH
1
ar), 8.62 (d, J = 6.0 Hz, 2H, CH ar); C (CDCl , 75
H, CH ar), 7.48–7.51 (m, 2H, CH ar), 7.6 (dd,
(
CH ), 30.2 (CH ), 30.8 (CH ), 55.2 (OCH ), 112.6
2 2 2 3
(
1
(
CH ar), 112.8 (CH ar), 119.2 (CH ar), 121.0 (CH),
24.3 (CH ar), 127.1 (CH ar), 129.2 (CH ar), 136.0
CH ar), 144.8 (Cq ar), 147.5 (C ), 149.2 (CH ar),
3
3
MHz): d 13.8 (CH ), 22.7 (CH ), 30.2 (CH ), 30.9
3
2
2
q
(
CH ), 123.5 (2 CH ar), 124.8 (CH), 125.5 (CH ar),
2
1
57.0 (C ar), 159.6 (C ar); GC (130 °C, 1 min, 20
q
q
1
(
25.9 (CH ar), 126.1 (CH ar), 126.3 (CH ar), 127.6
CH ar), 128.1 (CH ar), 128.2 (CH ar), 133.0 (C ar),
°
C/min, 250 °C): t = 8.6 min; MS (EI, m/z): 267
R
+ + +
Å
(
M) , 252 (MꢀCH ) , 238 (MꢀC H ) , 224
q
3
2
5
+
+Å
1
1
°
33.4 (C ar), 139.7 (C ar), 145.8 (C ar), 147.2 (C ),
q q q q
(
C H NO: 267.1623. Found 267.1626.
MꢀC H ) ; HRMS-EI: (M) . Calculated for
3
7
49.9 (2 CH ar); GC (130 °C, 1 min, 20 °C/min, 250
C): t = 13.8 min.
R
1
8
21
4
.1.9. (E)-2-[2-(2-naphthyl)-1-hexenyl]pyridine (9c)
1
H NMR (CDCl , 300 MHz): d 0.87 (t, J = 7.2 Hz,
4.1.12. (E)-[2-(4-bromophenyl)-1-phenyl-vinyl]trimeth-
ylsilane, (E)-[2-(4-bromophenyl)-2-phenyl-vinyl]tri-
methylsilane (15a,b)
3
3
J = 7.4 Hz, 2H, CH ), 6.89 (s, 1H, CH), 7.13 (ddd,
J = 7.5, 4.9, 1.1 Hz, 1H, CH ar), 7.34 (dd, J = 7.8, 0.8
Hz, 1H, CH ar), 7.46–7.53 (m, 2H, CH ar), 7.65–7.70
H, CH ), 1.34–1.52 (m, 4H, 2 CH ), 3.19 (appt,
3
2
2
1
H NMR (CDCl , 300 MHz): d ꢀ0.08 (s, 9H,
3
Si(CH ) ), ꢀ0.03 (s, 9H, Si(CH ) ), 6.31 (s, 1H, CH),
3
3
3 3
1
7.11–7.53 (m, 19H, CH and CH ar); C (CDCl , 75
3
(
J = 1.1, 0.6 Hz, 1H, CH ar), 8.68 (ddd, J = 4.7, 1.7,
m, 2H, CH ar), 7.84–7.90 (m, 3H, CH ar), 7.98 (dd,
3
MHz): d ꢀ0.7 (Si(CH ) ), 0.0 (Si(CH ) ), 120.4 (C ),
3
3
3 3
q
1
3
0
.8 Hz, 1H, CH ar); C (CDCl , 75 MHz): d 13.9
120.7 (C ), 125.1 (CH ar), 126.3 (2 CH ar), 126.4 (2
q
3
(
(
1
(
CH ), 22.8 (CH ), 30.0 (CH ), 30.9 (CH ), 121.0
3
CH ar), 127.0 (CH ar), 127.2 (2 CH ar), 127.3 (2 CH
ar), 129.5 (2 CH ar), 129.7 (CH ar), 130.3 (2 CH ar),
130.6 (2 CH ar), 138.1 (C ), 140.8 (C ), 142.0 (C ),
2
2
2
CH), 124.3 (CH ar), 125.1 (CH ar), 125.5 (CH ar),
25.9 (CH ar), 126.1 (CH ar), 127.5 (CH ar), 127.7
CH ar), 127.9 (CH ar), 128.2 (CH ar), 132.9 (C ar),
q
q
q
142.7 (CH ar), 146.1 (C ), 147.5 (C ), 155.0 (C ); GC
q q q
q
1
1
33.5 (C ar), 136.0 (CH ar), 140.7 (C ar), 147.5 (C ),
q
(150 °C, 1 min, 20 °C/min, 250 °C): t = 6.4 min, 6.7
q
q
R
+ +
Å
49.3 (CH ar), 157.1 (C ar); GC (130 °C, 1 min, 20
min; MS (EI, m/z): 332, 330 (M) , 317, 315 (MꢀCH ) .
q
3

E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
3829
1
3
4.1.13. (E)-[2-(4-bromophenyl)-1-(2-methylphenyl)-vi-
nyl]trimethylsilane, (E)-[2-(4-bromophenyl)-2-(2-meth-
Hz, 2H, CH ar); C (CDCl , 75 MHz): d 0.0 (Si(CH ) ),
3 3 3
13.8 (CH ), 22.6 (CH ), 31.2 (CH ), 34.4 (CH ), 124.9 (2
3 2 2 2
ylpheny)-vinyl]trimethylsilane (15c,d)
1
CH ar), 125.3 (q, J = 164 Hz, CF ), 126.3 (2 CH ar),
3
H NMR (CDCl , 300 MHz): d ꢀ0.09 (s, 9H,
129.0 (q, J = 32 Hz, CH ar), 130.2 (CH ar), 147.4 (C
1
3
q
9
Si(CH ) ), 0.00 (s, 9H, Si(CH ) ), 2.09 (s, 3H, CH ),
3
ar), 156.4 (Cq); F NMR (CDCl , 282 MHz): d
3
3 3
3
3
2
1
.27 (s, 3H, CH ), 5.82 (s, 1H, CH), 6.95–7.14 (m,
3
ꢀ62.4; GC (70 °C, 1 min, 20 °C/min, 250 °C): t = 7.0
R
1
3
+Å
+
7H, CH and CH ar); C (CDCl , 75 MHz): d 0.0
min; MS (EI, m/z): 300 (M) , 285 (MꢀCH ) , 281
+Å
16 23 3
3
3
+
(
Si(CH ) ), 0.2 (Si(CH ) ), 20.1 (CH ), 20.2 (CH ),
3
(MꢀF) ; HRMS-EI: (M) . Calculated for C H F Si:
3
3 3
3
3
1
1
20.9 (C ), 121.1 (C ), 125.0 (CH ar), 125.2 (CH ar),
q
300.1521. Found 300.1527.
q
25.5 (CH ar), 127.0 (CH ar), 127.2 (CH ar), 129.1
(
CH ar), 129.6 (CH ar), 129.8 (2 CH ar), 130.0 (CH
ar), 130.2 (2 CH ar), 130.6 (2 CH ar), 130.7 (2 CH
ar),133.6 (CH ar), 133.8 (C ), 134.7 (C ), 138.4 (C ),
Acknowledgements
q
q
q
1
41.7 (C ), 142.9 (CH ar), 144.8 (C ), 145.7 (C ), 147.9
q q q
E. Genin is grateful to the Ecole Normale Sup e´ rieure
de Paris for a Grant (2003–2004). We are also thankful
to M.-N. Rager (Ecole Nationale Sup e´ rieure de Chimie
de Paris) for NOESY experiments.
(
C ), 156.9 (C ); GC (150 °C, 1 min, 20 °C/min, 250
q
q
°
C): t = 6.6 min, 7.0 min; MS (EI, m/z): 346, 344
R
+
Å
+
(
M) , 331, 329 (MꢀCH ) .
3
4.1.14. (E)-[2-(4-bromophenyl)-1-(3-methoxyphenyl)-
vinyl]trimethylsilane, (E)-[2-(4-bromophenyl)-2-(3-
References
methoxyphenyl)-vinyl]trimethylsilane (15e,f)
1
H NMR (CDCl , 300 MHz): d ꢀ0.05 (s, 9H,
3
[
[
1] B. Cornils, W.A. Herrmann, in: Applied Homogeneous Catalysis
with Organometallic Compound, VCH, New York, 1996.
2] (a) P.A. Grieco (Ed.), Organic Synthesis in Water, Blacky
Academic and Professional, London, 1998;
Si(CH ) ), 0.00 (s, 9H, Si(CH ) ), 3.79 (s, 3H, CH ),
3
3
3 3
3
3
1
.86 (s, 3H, CH ), 6.35 (s, 1H, CH), 6.79–7.53 (m,
3
1
3
7H, CH and CH ar); C (CDCl , 75 MHz): d 0.0
3
(
1
(
5
1
Si(CH ) ), 0.7 (Si(CH ) ), 55.1 (OCH ), 55.2 (OCH ),
11.1 (CH ar), 112.9 (CH ar), 113.0 (CH ar), 113.1
(b) C.-J. Li, T.-H. Chan (Eds.), Organic Reactions in Aqueous
Media, Wiley, New York, 1997;
3
3
3 3
3
3
(
c) B. Cornils, W.A. Herrmann (Eds.), Aqueous-phase Organo-
CH ar), 119.6 (CH ar), 119.8 (CH ar), 121.2 (C ), 121
q
metallic Catalysis, Wiley-VCH, New York, 1998.
3] For recent reviews, see: (a) N. Pinault, D.W. Bruce, Coord.
Chem. Rev. 241 (2003) 1;
(C ), 128.9 (CH ar), 129.0 (CH ar), 130.2 (2 CH ar),
q
[
30.6 (CH ar), 131.0 (4 CH ar), 131.3 (2 CH ar), 138.7
(
(
C ), 141.4 (C ), 143.3 (CH ar), 144.3 (CH ar), 148.0
q
(b) C.-J. Li, Acc. Chem. Res. 35 (2002) 533;
q
(
(
c) C.-J. Li, T.H. Chan, Tetrahedron 55 (1999) 11149;
d) A. Lubineau, J. Aug e´ , in: P. Knochel (Ed.), Modern Solvent
C ), 148.1 (C ), 155.6 (C ), 159.3 (C ), 159.4 (C );
q
q
q
q
q
GC (150 °C, 1 min, 20 °C/min, 250 °C): t = 8.0, 8.5
min.
R
in Organic Synthesis, Topics in Current Chemistry, vol. 206,
Springer, Berlin, 1999, p. 1;
(
e) D. Sinou, in: P. Knochel (Ed.), Modern Solvent in Organic
Synthesis, Topics in Current Chemistry, vol. 206, Springer, Berlin,
999, p. 41;
(f) A. Lubineau, J. Aug e´ , Y. Queneau, Synthesis (1994) 741;
g) W.A. Herrmann, C.W. Kohlpaintner, Angew. Chem. Int., Ed.
Engl. 32 (1993) 1524.
[4] Abbreviations: TPPTS = trisodium salt of 3,3 ,3 -phosphanetriyl-
4
.1.15. (E)-2-(4-methoxyphenyl)-1-(trimethylsilyl)-1-
hexene (18b)
1
1
H NMR (CDCl , 300 MHz): d 0.20 (s, 9H,
3
(
Si(CH ) ), 1.32 (t, J = 7.0 Hz, 3H, CH ), 1.33–1.36 (m,
4H, 2 CH ), 2.57–2.62 (m, 2H, CH ), 3.82 (s, 3H,
OCH ), 5.68 (s, 1H, CH), 6.85 (d, J = 8.9 Hz, 2H, CH
1
ar), 7.35 (d, J = 8.9 Hz, 2H, CH ar); C (CDCl , 75
3
3
3
0
00
2
2
0
00
benzenesulfonic acid, TPPTC = trilithium salt of 3,3 ,3 -phos-
phanetriylbenzenecarboxylic acid, TPPDS = dipotassium salt of
3
3
3
0
4,4 -phosphanediylbenzenesulfonic acid.
5] (a) E.G. Kuntz, Chemtech (1987) 570;
MHz): d 0.0 (Si(CH ) ), 13.7 (CH ), 22.6 (CH ), 31.4
3
3
3
2
[
(
CH ), 34.4 (CH ), 54.9 (OCH ), 113.1 (2 CH ar),
2 2 3
(
b) B. Cornils, E.G. Kuntz, J. Organomet. Chem. 502 (1995) 177;
1
1
25.6 (CH), 126.9 (2 CH ar), 135.8 (C ), 156.7 (C ar),
q q
(c) E.G. Kuntz, O.M. Vittori, J. Mol. Catal. A: Chem. 129 (1998)
159;
58.5 (C ar); GC (70 °C, 1 min, 20 °C/min, 250 °C):
q
+
Å
+
(
d) B.M. Bhanage, S.S. Divekar, R.M. Deshpande, R.V. Chaud-
hari, Org. Proc. Res. Dev. 4 (2000) 342;
e) T. Bartik, B. Bartik, B.E. Hanson, T. Glass, W. Bebout,
Inorg. Chem. 31 (1992) 2667;
f) W.A. Herrmann, G.P. Albanese, R.B. Manetsberger, P. Lappe,
H. Bahrmann, Angew. Chem. Int., Ed. Engl. 34 (1995) 811;
g) B.M. Bhanage, F.-G. Zhao, M. Shirai, M. Arai, Tetrahedron
t = 14.0 min; MS (EI, m/z): 262 (M) , 247 (MꢀCH ) ;
R
3
+
HRMS-EI: (M) . Calculated for C H O: 262.1753.
Å
1
6
26
(
Found 262.1748.
(
4
hexene (18c)
.1.16.
(E)-2-(4-trifluorophenyl)-1-(trimethylsilyl)-1-
(
1
Lett. 39 (1998) 9509 and references cited therein.
6] V. Michelet, M. Savignac, J.-P. Gen eˆ t, Electronic encyclopedia of
reagents for organic synthesis, 2004 (in press).
H NMR (CDCl , 300 MHz): d 0.20 (s, 9H,
3
[
Si(CH ) ), 0.88 (t, J = 6.9 Hz, 3H, CH ), 1.28–1.33 (m,
3
3
3
4H, 2 CH ), 2.60–2.65 (m, 2H, CH ), 5.79 (s, 1H,
2 2
CH), 7.47 (d, J = 8.1 Hz, 2H, CH ar), 7.56 (d, J = 8.1
[7] (a) H. Dibowski, F.P. Schmidtchen, Angew. Chem. Int., Ed.
Engl. 37 (1998) 476;

3
830
E. Genin et al. / Journal of Organometallic Chemistry 689 (2004) 3820–3830
b) M.P. Leese, J.M.J. Williams, Synlett (1999) 1645 and [22] E. Shirakawa, G. Takahashi, T. Tsuschimoto, Y. Kawakami,
(
references cited therein;
Chem. Commun. (2001) 2688.
[23] V. Launey, I. Beaudet, J.-P. Quintard, Synlett (1997)
821.
(
c) T. Thorpe, S.M. Brown, J. Crosby, S. Fitzjohn, J.P.
Muxworthy, J.M.J. Williams, Tetrahedron Lett. 41 (2000) 4503;
d) A. Hessler, O. Stelzer, H. Dibowski, K. Worm, F.P.
Schmidtchen, J. Org. Chem. 62 (1997) 2362;
e) M. Lautens, A. Roy, F. Fukuoka, K. Fagnou, B. Martin-
Matute, J. Am. Chem. Soc. 123 (2001) 5358.
8] (a) J.-P. Gen eˆ t, M. Savignac, J. Organomet. Chem. 576 (1999)
05;
b) J.-P. Gen eˆ t, M. Savignac, S. Lemaire-Audoire, in: S.-I.
(
[24] (a) Y. Misumi, T. Masuda, Macromolecules 31 (1998) 7572;
(b) M. Yamamoto, K. Onitsuka, S. Takahashi, Organometallics
19 (2000) 4669.
(
[25] (a) For a recent review on Rh-catalyzed reactions, see: K. Fagnou,
M. Lautens, Chem. Rev. 103 (2003) 169;
[
[
3
(b) R. Itooka, N. Miyaura, J. Org. Chem. 68 (2003) 6000;
(c) M. Lautens, A. Roy, F. Fukuoka, K. Fagnou, B. Martin-
Matute, J. Am. Chem. Soc. 123 (2001) 5358;
(
Murahashi, S.G. Davies (Eds.), IUPAC Monographs ‘‘Chemistry
for the 21st Century’’ Transition Metal Catalysed Reactions,
(d) A. F u¨ rstner, H. Krause, Adv. Synth. Catal. 343 (2001) 343.
[26] (a) M. Pucheault, S. Darses, J.-P. Gen eˆ t, Tetrahedron Lett. 43
(2002) 6155;
1
999, p. 55.
9] (a) C. Amatore, E. Blart, J.-P. Gen eˆ t, A. Jutand, S. Lemaire-
Audoire, M. Savignac, J. Org. Chem. 60 (1995) 6829;
(b) M. Pucheault, S. Darses, J.-P. Gen eˆ t, Eur. J. Org. Chem.
(2002) 3552;
(
b) C. Dupuis, K. Adiey, L. Charruault, V. Michelet, M. Savignac,
J.-P. Gen eˆ t, Tetrahedron Lett. 42 (2001) 6523.
10] J.-C. Galland, M. Savignac, J.-P. Gen eˆ t, Tetrahedron Lett. 40
1999) 2323.
(c) L. Navarre, S. Darses, J.-P. Gen eˆ t, Angew. Chem. Int., Ed.
Engl. 43 (2004) 719.
[
[
[
(
[27] The requisite substituted alkynes have been prepared by Sono-
gashiraÕs cross-couplings (unpublished results).
[28] (a) F. Babudri, G.M. Farinola, L.C. Lopez, M.G. Martinelli, F.
Naso, J. Org. Chem. 66 (2001) 3878;
11] V. Michelet, J.-C. Galland, L. Charruault, M. Savignac, J.-P.
Gen eˆ t, Org. Lett. 3 (2001) 2065.
12] (a) C. Nevado, L. Charruault, V. Michelet, C. Nieto-Oberhuber,
M.P. Munoz, M. Mendez, M.-N. Rager, J.-P. Gen eˆ t, A.M.
Echavarren, Eur. J. Org. Chem. (2003) 706;
(b) F. Babudri, G.M. Farinola, F. Naso, D. Panessa, J. Org.
Chem. 65 (2000) 1554;
(
(
(
b) L. Charruault, V. Michelet, J.-P. Gen eˆ t, Tetrahedron Lett. 43
2002) 4757;
(c) F. Babudri, G.M. Farinola, V. Fiandanese, L. Mazzone, F.
Naso, Tetrahedron 54 (1998) 1085;
c) J.-C. Galland, S. Diaz, M. Savignac, J.-P. Gen eˆ t, Tetrahedron
(d) F. Babudri, A.R. Cicciomessere, G.M. Farinola, V. Fianda-
nese, G. Marchese, R. Musio, F. Naso, O. Sciacovelli, J. Org.
Chem. 62 (1997) 3291;
57 (2001) 5137;
(
(
d) J.-C. Galland, M. Savignac, J.-P. Gen eˆ t, Tetrahedron Lett. 38
1997) 8695.
(e) K. Ikegashira, Y. Nishihara, K. Hirabayashi, A. Mori, T.
Hiyama, Chem. Commun. (1997) 1039;
[
[
[
[
13] R. Amengual, E. Genin, V. Michelet, M. Savignac, J.-P. Gen eˆ t,
Adv. Synth. Catal. 344 (2002) 393.
(f) Y. Nishihara, K. Ikegashira, K. Hirabayashi, J. Ando, A.
Mori, T. Hiyama, J. Org. Chem. 65 (2000) 1780;
(g) S. Denmark, Z. Wang, Synthesis (2000) 999.
[29] The hydrolysis of the vinylrhodium intermediate by the boronic
acid was negligible (5% of protic source).
14] R. M e´ tivier, R. Amengual, I. Leray, V. Michelet, J.-P. Gen eˆ t,
Org. Lett 6 (2004) 739.
15] R. Amengual, V. Michelet, J.-P. Gen eˆ t, Tetrahedron Lett. 43
(
2002) 5905.
16] (a) R. Amengual, V. Michelet, J.-P. Gen eˆ t, Synlett (2002) 1791;
b) For a recent review on asymmetric 1,4-addition, see:T.
[30] The syn addition to the alkyne was based on the same analytical
1
analysis of 2a from literature [17] and on NOESY H NMR
(
Hayashi, K. Yamasaki, Chem. Rev. 103 (2003) 2829.
17] T. Hayashi, K. Inoue, N. Taniguchi, M. Ogasawara, J. Am.
Chem. Soc. 123 (2001) 9918.
experiments for alkenes 3a, 11a, 18a.
[31] For recent concentration controls in water or fluorous systems,
see: (a) I. Ryu, H. Matsubara, S. Yasuda, H. Nakamura, D.P.
Curran, J. Am. Chem. Soc. 124 (2002) 12946;
(b) J. Xiang, A. Orita, J. Otera, Angew. Chem. Int., Ed. Engl. 41
(2002) 4117;
[
[
[
18] For a preliminary communication, see: E. Genin, V. Michelet, J.-
P. Gen eˆ t, Tetrahedron Lett. 45 (2004) 4157.
19] (a) SDS surfactant was advocated for the arylation of pyridyl
substituted alkynes:M. Lautens,M. Yoshida, Org. Lett. 4 (2002) 123;
(c) H. Kinoshita, H. Shinokubo, K. Oshima, J. Am. Chem. Soc.
125 (2003) 7784.
(
b) M. Lautens, M. Yoshida, J. Org. Chem. 68 (2003) 762.
20] (a) For the preparation of the [Rh(cod)OH]
see: R. Uson, L.A. Oro, J. Cabeza, Inorg. Synth. 23 (1985) 126;
b) For the use the [Rh(cod)OH] catalyst see:T. Hayashi, M.
Takahashi, Y. Takaya, M. Ogasawara, J. Am. Chem. Soc. 124
[
2
catalyst,
[32] K.A. Agrios, M. Srebnik, J. Organomet. Chem. 444 (1993)
15.
(
2
[33] Y. Gao, K. Harada, T. Hata, H. Urabe, F. Sato, J. Org. Chem.
60 (1995) 290.
(
(
(
2002) 5052;
c) T. Fujii, T. Koike, A. Mori, K. Osakada, Synlett (2002) 295;
d) A. Mori, Y. Danda, T. Fujii, K. Hirabayashi, K. Osakada, J.
[34] V.P. Balema, J.W. Wiench, M. Pruski, V.K. Pecharsky, J. Am.
Chem. Soc. 124 (2002) 6244.
[35] T. St u¨ demann, M. Ibrahim-Ouali, P. Knochel, Tetrahedron 54
(1998) 1299.
Am. Chem. Soc. 123 (2001) 10774.
21] The 2a/3a ratio was determined by H NMR analysis and gas
chromatography. No traces of trimer were detected.
1
[
[36] S.-S.P. Chou, H.-L. Kuo, C.-J. Wang, C.Y. Tsai, C.-M. Sun, J.
Org. Chem. 54 (1989) 868.