A novel water-soluble m-TPPTC ligand: Steric and electronic features - Recent developments in Pd- and Rh-catalyzed C-C bond formations

Article abstract of DOI:10.1002/adsc.200404218

The steric and electronic features of the novel water-soluble phosphane m-TPPTC have been determined using NMR, IR and UV-VIS spectroscopic methods and compared to the well-known sulfonated analogue TPPTS. The higher basicity of m-TPPTC compared to TPPTS

Full text of DOI:10.1002/adsc.200404218

FULL PAPERS
A Novel Water-Soluble m-TPPTC Ligand: Steric and Electronic
ꢀ
Features – Recent Developments in Pd- and Rh-Catalyzed C C
Bond Formations
Emilie Genin, R e´ mi Amengual, V e´ ronique Michelet,* Monique Savignac,*
Anny Jutand, Luc Neuville, Jean-Pierre Gen eˆ t*
Ecole Nationale Sup e´ rieure de Chimie de Paris, Laboratoire de Synth e` se S e´ lective Organique et Produits Naturels, UMR
7
573, 11 rue P. et M. Curie, 75231 Paris Cedex 05, France and Ecole Normale Sup´ er ieure, D e´ partement de Chimie, UMR
8640, 24 rue Lhomond, 75231 Paris Cedex 05, France
Fax: (þ33)-1-44-07-10-62, e-mail: michelet@ext.jussieu.fr, savignac@ext.jussieu.fr, genet@ext.jussieu.fr
Received: July 7, 2004; Accepted: October 15, 2004
Abstract: The steric and electronic features of the ized aryl iodides were efficiently performed using
novel water-soluble phosphane m-TPPTC have been the carboxylated phosphane m-TPPTC leading to
determined using NMR, IR and UV-VIS spectroscop- the alkynes in high yields. The Pd/m-TPPTC system
ic methods and compared to the well-known sulfonat- was found to be efficiently recycled under mild bipha-
ed analogue TPPTS. The higher basicity of m-TPPTC sic conditions in the Sonogashira reaction.
compared to TPPTS had an influence (selectivity and
efficiency) either on Pd- or Rh-catalyzed CꢀC bond Keywords: palladium; phosphane basicity; recycling;
formations reactions. The Sonogashira copper-free rhodium; Sonogashira cross-couplings; water-soluble
cross-couplings of aryl iodides and ortho-functional- ligand
Introduction
group reported the synthesis of amphiphilic phosphane
and showed that the palladium-catalyzed cleavage of
7
[7 h]
Over the past few years, significant research has been di- undecyl allyl carbonate was highly accelerated.
The
rected toward the development of new technologies for Lautens group prepared the sulfonated ligands 8a and
[
1]
environmentally benign processes. Among them, the 8b which offered a higher activity compared to the
[
10]
application of water as solvent in organic syntheses TPPTS ligand. Recently, we have reported a versatile
and in homogeneous transition-metal catalyzed reac- preparation of the water-soluble ligand m-TPPTC 4
[
1,2]
tions has been steadily growing. Indeed, water is not functionalized by carboxylated moieties, which presents
ꢀ
1
[6]
toxic and non-inflammable, the most attractive feature a very high solubility (1100 g·L ).
being its utility in the development of efficient environ- Preliminary studies on the Pd-catalyzed Heck reac-
mentally safe systems. The industrial hydroformylation tion of aryl iodides pointed out that this ligand displays
of propene in a biphasic system medium (water/organic) a high efficiency compared to its sulfonated analogue
[6]
using the water-soluble ligand TPPTS 1 by Rh oˆ ne–Pou- with some benefits in term of kinetics of the reactions.
lenc has stimulated the interest for new organometallic
[
3,4]
systems either for CꢀH or CꢀC bond formations. Sev-
[
5,6]
eral groups including ours have worked intensively in
finding new applications for the sulfonated ligand
TPPTS and in preparing new water-soluble analogues
of triphenylphosphane bearing anionic or cationic
[
7]
groups (Scheme 1). Various hydrosoluble ligands
[8]
[9]
[7c–d]
such as 2,
3
and 5
have been described and
showed interesting and similar properties in Pd-cata-
lyzed CꢀC bond formations compared to the well-
known TPPTS ligand. The Shaughnessy group describ-
ed the synthesis of a sterically demanding phosphane,
TXPTS 6, which showed a higher activity than the
[
7a]
TPPTS ligand for the Heck reaction. The Monflier Scheme 1.
Adv. Synth. Catal. 2004, 346, 1733–1741
DOI: 10.1002/adsc.200404218
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FULL PAPERS
Emilie Genin et al.
We also foundthat some Rh-catalyzed couplings, such as phosphane selenides derived from the reaction of a ter-
the addition of boronic acids to alkene and alkynes, were tiary phosphane and selenium was shown to be much de-
particularly effective in the presence of the m-TPPTC li- pendent upon the nature of the organic groups bound to
[11]
[13,15]
gand. Indeed, the use of the m-TPPTC ligand allowed phosphorus.
Electron-withdrawing groups on phos-
better results in terms of activity, selectivity compared to phorus will cause the coupling constant to increase
its sulfonated analogue TPPTS. In the meantime, these whereas electron-donating groups and bulky groups
results prompted us to investigate the steric and elec- will cause it to decrease. The phosphane selenides
tronic properties of our new ligand. We report herein were obtained via the reaction of the corresponding li-
the stereoelectronic properties of the carboxylated li- gands with an excess of selenium in refluxing ethanol.
gand m-TPPTC, and some applications in palladium- As the bulkiness was identical for the sulfonated and
1
77
31
and rhodium-catalyzed reactions including the recycling the carboxylated ligands, the J ( Se- P) value differen-
of the [Pd]/m-TPPTC catalysts.
ces could be attributed to a better donor ability for the
m-TPPTC ligand. The same trend was observed when
measuring the n(CO) stretching frequency by infra-red
[
7g,16]
Results and Discussion
spectroscopy of the complexes cis-(CO) MoL ,
de-
4
2
rived from norbornadiene(tetracarbonyl)molybdenum
and the corresponding ligands m-TPPTC or TPPTS. Fi-
nally, a method based on a Pd formation kinetic study
Steric and Electronic Features of the m-TPPTC
Ligand
0
described by Jutand and Amatore also attracted our at-
[
17]
tention. In the course of their study of the Heck mech-
In order to get information about the influence of the anism, they also showed that the formation of the palla-
carboxy group on the ligand, we decided to evaluate dium(0) complex was sensitive to electronic and steric
the steric parameters and the electronic properties on factors of the phosphane used to generate it. Consider-
phosphorus and the acid-base profile of the substituents. ing the same bulk environment of para-substituted triar-
These data may indeed have a crucial influence on the ylphosphanes, they reported that the more the triaryl-
exit of the reaction catalyzed by their transition metal phosphane is substituted by electron-withdrawing
complexes. To evaluate the bulkiness generated by the groups, the faster the reaction is. Therefore, to ascertain
phosphane, we turned our attention towards a method the electronic properties of our new ligand compared to
that proved to be valuable for substituted triarylphos- the TPPTS ligand, and as we were studying various Pd-
31
phanes. It has been shown that the PNMR chemical
catalyzed cross-coupling reactions, we decided to deter-
shift of trans-(PAr ) PdCl complexes correlates well mine the rate constant of the formation of palladium(0)
3
2
2
with the bulkiness of phosphane ligands such as TPPTS complexes. Moreover, as the ligands display the same
[7 g]
[12]
and GUAPHOS, for example. The palladium com- hindrance, the measurement of the rate constant would
plex derived from the carboxylated ligand m-TPPTC give us additional information on the electronic proper-
was commonly prepared by the reaction of bis(benzoni- ties of both ligands. The proposed mechanism for the
0
trile)palladium dichloride and 2 equivalents of phos- formation of the Pd complex implies a fast complexa-
phane in a CH Cl /H O mixture. For a better compari- tion of the ligand PAr leading to Pd(OAc) (PAr ) ,
2
2
2
3
2
3 2
son, the same experiment was conducted with the which slowly evolves to a palladium(0) complex
ꢀ
TPPTS ligand and the result was in good accordance [Pd(OAc)(PAr )] (Scheme 2). The last step consists
3
ꢀ
with literature reports. As presented in Table 1 and as of the formation of [Pd(OAc)(PAr ) ] .
3
3
expected, the carboxylated and the sulfonated ligands
have a similar cone angle and therefore generate the
[13]
same steric bulk. It is noteworthy that the effective
bulk of these ligands is significantly larger than that of
triphenylphosphane (qTol ¼1458), due to the presence
of meta substituents.
Concerning the electronic properties of our phos-
phane, general and simple methods have been described
in the literatureto assess the s-donor/p-acceptor charac-
[
14]
1
77
31
ter of the phosphane. The magnitude of J( Se- P ) in
Scheme 2.
Table 1. Electronic and steric parameters for the carboxylated ligand m-TPPTC compared to TPPTS.
3
1
1
ꢀ1
Ligand
trans-PdCl L d P[ppm]
qTol [8]
Se¼PAr3 JP-Se [Hz]
cis-Mo(CO) L n [cm ]
4 2 CO
2
2
m-TPPTC
TPPTS
34.1
34.3
166
166
733
757
2020
2025
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A Novel Water-Soluble m-TPPTC Ligand
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0
Figure 3. Kinetics of formation of the Pd complex generated
0
Figure 1. Absorbance data of the Pd complex generated
from Pd(OAc) (3.3 mM) and 10 equivalents of TPPTS in a
/1 NMP/ethylene glycol system: variation of ln((AlꢀA)/Al)
2
from Pd(OAc) (3.3 mM) and 10 equivalents of m-TPPTC
in a 1/1 NMP/ethylene glycol system at various times.
2
1
as a function of time.
0
Figure 2. Kinetics of formation of the Pd complex from
Pd(OAc) (3.3 mM) and 10 equivalents of m-TPPTC in a
2
1
/1 NMP/ethylene glycol system: variation of ln((AlꢀA)/Al)
Figure 4. Potentiometric titration curves for the carboxylated
m-TPPTC phosphane and the sulfonated TPPTS ligand.
as a function of time.
We attempted to observe the formation of zero-valent
These results show that the formation of the palladi-
palladium using cyclic voltammetry, but no reproducible um(0) complex is favored with the sulfonated ligand
cyclic voltammograms were obtained. The formation of compared to the carboxylated one. Consequently, as
0
the Pd species was therefore observed by UV-VIS spec- the rate-determining step can be assimilated to a reduc-
troscopy at room temperature. The UV absorbance of tion, the m-TPPTC phosphane is more electron-rich
0
ꢀ
3
[
Pd (OAc)(PAr ) ] (l¼430 nm) increased stepwise than TPPTS.
3
upon mixing Pd(OAc) and the respective triarylphos-
phane m-TPPTC (Figure 1) or TPPTS. The rate con- according to the procedure described by Bartik et al.
We also determined the pK values of the phosphanes
a
2
[18]
stants were determined by plotting the variation of Figure 4 shows the overlaid titration curves for both the
ln((A1–A)/A1) as a function of time, where Al is the ab- TPPTS and the m-TPPTC ligand. The potentiometric
sorbance at infinite time and A the absorbance at time t. measurements were recorded in the course of the addi-
These data afforded a straightline (first-order kinetics in tion of an aqueous solution of sodium hydroxide to an
palladium species), the slope providing directly the rate acidified water-solution of the m-TPPTC or TPPTS li-
0
constant of Pd formation. From the experimental val- gands. As already described by Bartik, the sulfonated li-
ꢀ
ꢀ
4
3
ꢀ1
ꢀ1
ues, the rate constants were found to be 1.8·10
for the m-TPPTC ligand (Figure 2) and 5.3·10
for the TPPTS ligand (Figure 3).
s
s
gand shows a unique acidity for the three sulfonated
functionalities (pK ¼2.1). The carboxylated phosphane
a
displays a different behavior as buffering plateaus are
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Emilie Genin et al.
observed. The first wave corresponds to the titration of
two carboxylic groups (pK ¼2.2), whereas the second
a
wave corresponds to the titration of the third more ba-
sic carboxylic group (pK ¼5.3). This higher basicity
a
may therefore influence the global basicity of the phos-
phane.
Scheme 3.
Pd-Catalyzed Sonogashira Reactions – Rh-Catalyzed
Arylation of Alkynes
Having in hand a new water-soluble ligand displaying in-
teresting electronic properties, we decided to extend its
area of metal-catalyzed applications. We turned our at-
tention to the Sonogashira coupling of aryl halides,
which constitutes one of the most powerful and mild
[
19]
[20]
methods for the creation of CꢀC bonds. We and
[21,22]
Scheme 4.
others had reported that copper salts were not com-
pulsory for such cross-coupling in the presence of the
water-soluble ligand TPPTS. Functionalized 2-amino-
or 2-hydroxyaryl iodides appear to be of interest to com-
pare the selectivity between the sulfonated and the car-
boxylated ligands as it was reported (Scheme 3) that the
cross-couplings of such substrates led either to a mixture
of 9 and 10 in favor of the cyclized product 9 (X¼NH) or
[
20b]
to the benzofuran (X¼O).
The formation of ortho-
functionalized alkynes, indoles and benzofurans consti-
tutes an access to important building blocks for the syn-
thesis of natural and biologically active compounds.
[
23]
We were pleased to find that the couplings were as ef-
ficient with m-TPPTC as with the TPPTS ligand and
were able to decrease the mole fraction of palladium
to 1 mol % using either triethylamine (Conditions A)
or diisopropylamine (Conditions B) as exemplified in
Table 2. The reaction of 2-iodoanilines with various al-
Scheme 5.
The cross-couplings were as expected highly efficient
kynes afforded this time exclusively the linear products with 2-iodoanilines bearing electron-withdrawing
1
0a–d, with no traces of the cyclized indoles (entries 1– groups. The corresponding functionalized alkynes 10i,
4
). The isolated yields were generally good with unpro- 10j were isolated in 83% and 90% yields (Scheme 4).
[
24]
tected anilines 10a and 10b (entries 1 and 2) and quite
These results on the Sonogashira cross-couplings
modest with the acetyl-protected substrates 10c and therefore illustrate the specific selectivity generated by
0d (entries 3 and 4). The Sonogashira cross-coupling/ the use of the m-TPPTC ligand. Similarly to its sulfonat-
[
25]
1
intramolecular cyclization sequence was observed in ed analogue TPPTS, no copper salts are necessary to en-
the case of the oxygenated compounds, as the function- able the reaction. Nevertheless, a different selectivity is
[
26a]
[26b]
alized benzofurans 9e
and 9f
were respectively observed as the reaction of 2-aminoaryl iodides affords
isolated in 80% and 60% yields (entries 5 and 6). This the classic linear adduct in the presence of the m-TPPTC
substrate dependence observation was quite surprising phosphane, or the indole derivative in the presence of
considering the nucleophilicity of oxygen and nitro- the TPPTS ligand. One plausible explanation may in-
[24,27]
gen.
One reasonable explanation may be that the volve the intrinsic properties and the differences of
phenol moiety is partially deprotonated under the basic both ligands. The well-accepted catalytic cycle for the
reaction conditions and therefore may attack across the formation of the linear derivative involves a classic oxi-
II
CꢀC triple bond, activated by the coordination to a Pd
dative addition leading to the Ar-[PdL ]-I, then a trans-
n
complex. This could be confirmed when subjecting the metallation presumably generated via an alkynylpalla-
benzylic substrates to the same conditions (entries 7 dium intermediate and finally a reductive elimination
[
28a]
[20b]
and 8). The corresponding linear alcohols 10g
and to create the substituted alkyne.
were this time obtained in good yields (68 and may then occur through a first activation of the function-
7%) and no traces of the cyclized adducts were detect- alized alkyne followed by a nucleophilic attack of the
The cyclization
[28b]
10h
8
ed.
[
23,27]
amino group (Scheme 5).
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A Novel Water-Soluble m-TPPTC Ligand
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Table 2. Sonogashira cross-couplings of ortho-substituted aryl iodides.
[a]
Entry
1
R
R’
t [h]
Product
20
Conditions
B
Yield [%]
85
NH2
P
h
10a
10b
2
NH2
CMe OH
22
A
80
2
3
4
NHAc
NHAc
Ph
20
20
10c
10d
B
B
20
22
4-Br-C H
6
4
5
6
7
OH
OH
P
h
20
9e
B
B
A
81
60
87
CMe OH
20
16
9f
2
CH OH
Ph
10g
2
8
CH OH
CMe OH
16
10h
A
68
2
2
[
a]
Isolated yields.
[
11]
The ability of the catalytic system to perform or not trisubstituted alkenes. Using only 1 mol % palladium
the cyclization step on 2-iodoaniline may come from at 708C in acetonitrile/water mixture and without a cop-
the reactivity of the intermediate A. Having shown per co-catalyst (Scheme 6), the 2-(1-hexynyl)pyridine
that the m-TPPTC ligand is more basic than the TPPTS
phosphane, the electron density transfer is higher in the
case of the carboxylated ligand, which therefore disfa-
vors the formation of indoles.
We took advantage of the high efficiency of the water-
soluble ligand m-TPPTC and prepared other useful al-
kynes via Sonogashira cross-couplings (Scheme 6).
Functionalized alkynes are important building blocks
to prepare a wide variety liquid crystals, conducting poly-
[
29]
mers and other engineering materials. For example,
precursors of novel fluorophores had been reported re-
[30]
cently. The pyridinyl and thiophenyl derivatives were
also synthesized in the same way and were evaluated for
Rh-catalyzed regio- and stereoselective preparations of Scheme 6. Preparation of substituted alkynes.
Adv. Synth. Catal. 2004, 346, 1733–1741
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Emilie Genin et al.
Table 3. Rh-catalyzed arylation of alkynes with phenylboronic acid.
[a]
Entry
Ligand
R
R’
Solvent
Ratio of 14/15
Yield [%]
1
2
3
4
5
6
m-TPPTC
m-TPPTC
TPPTS
TPPTS
m-TPPTC
TPPTS
C H
C H
H O
80/20
98/2
60/40
85/15
96/4
95
90
63
89
95
60
3
7
7
7
7
3
7
7
7
7
2
C H
C H
H O/toluene
3
3
2
C H
C H
H O
3
3
2
C H
C H
H O/toluene
3
3
2
Ph
Ph
Me
Me
H O/toluene
2
H O/toluene
2
70/30
[
a]
Isolated yields.
nation to 15. As the m-TPPTC ligand is more basic
than the sulfonated phosphane TPPTS, the second com-
plexation of the alkyne leading to C is disfavored, which
brings about a better alkene/diene ratio.
Having shown a remarkable activity and selectivity of
the m-TPPTC ligand, we further pursue our study by
testing the recyclability of the [Pd]/m-TPPTC system.
Scheme 7.
[10a]
[10a]
11
and 4-(1-hexynyl)pyridine 12
were isolated in
good yields (75–85%). The 2-(1-phenyl)thiophene A Recyclable Pd/m-TPPTC System
[31]
[32]
1
3a and 2-(1-hexynyl)thiophene 13b were also ob-
tained in good to excellent yields and in shorter reaction A major challenge in homogeneous catalysis is to permit
time and temperature. the simple isolation of products from economical and in-
Anticipating that the differences between the m- dustrial viewpoints. Recyclable catalysts constitute a
TPPTC and TPPTS may be observed with other organo- good alternative to the product/catalyst separation and
metallic species, we compared their reactivity through to the use of low mole fractions of expensive transition
the Rh-catalyzed arylation of alkynes. We recently de- metals. A key advantage of a water-soluble phosphane
[
1–5]
scribed the Rh-catalyzed addition of boronic acids to lies in the recycling possibility of the catalyst.
De-
substituted alkynes in water and in biphasic media using spite the widespread studies towards recyclable catalysts
[
11]
the m-TPPTC ligand, which provides a convenient for the metal-catalyzed formation of CꢀC bonds, there
preparation of trisubstituted alkenes in excellent yields are only scarce examples described in the literature for
[
21,33]
and purity. The addition of phenylboronic acid to oct- the Sonogashira reaction.
In most cases, an efficient
4-yne led to an 80/20 alkene 14 to diene 15 ratio in a recycling could be performed using 5 mol % catalyst,
very good 95% yield (entry 1, Table 3). In biphasic con- high temperature or/and long reaction time. We ex-
ditions, the reaction was found to be highly selective in plored the recyclability of our Pd(OAc) /m-TPPTC sys-
2
favor of the alkene 14 (entry 2).
tem in the reaction of 2-iodothiophene with phenylace-
The use of the TPPTS ligand gave quite different out- tylene under mild conditions at 408C. The acetonitrile/
comes in term of efficiency (entry 3) and selectivity (en- water medium could be easily transposed to a biphasic
tries 3 and 4) whatever the solvent involved. The same butyronitrile/water system. As shown in Figure 5, four
trend was observed with 1-phenylpropyne (entries 5 cycles were performed using only 1 mol % of the cata-
and 6). The use of the carboxylated ligand afforded high- lyst system. It is noteworthy that the reaction times
er yield and selectivity toward the desired trisubstituted were short for the three cycles (2.5–5 h) and needed
alkene 14.
to be increased to three days for the fourth cycle. After
In the same manner as previously, one may explain the completion of the reaction, the organic phase was sepa-
observed selectivity in view of the conceivable inter- rated, the aqueous phase was then extracted two times
mediates B and C (Scheme 7). The key intermediate C with butyronitrile and reloaded with substrates. The al-
may be either hydrolyzed to give the alkene 14 or may kyne was isolated with 98–99% yield and with excellent
complex another alkyne molecule leading after proto- purity (>95%).
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A Novel Water-Soluble m-TPPTC Ligand
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formed at the Ecole Nationale Sup e´ rieure de Chimie de Paris
with a Hewlett-Packard HP 5989 A. Direct introduction ex-
periments were done by electronic impact. All manipulations
were carried out under nitrogen and Schlenk techniques for
catalytic tests. Pd(OAc) was purchased from Acros. TPPTS
2
was generously given by Rhodia (France). Water, acetonitrile
and butyronitrile were degassed by sparging with nitrogen
and/or exposure to vacuum. Column chromatography was per-
formed with E. Merck 0.040–0.063 mm Art. 11567 silica gel.
Florisil (100–200 mesh) was purchased from Acros or Avoca-
[
24]
[25]
[26a]
[26b]
[11a]
do. The spectral data of alkynes 10a, 10c, 9e,
9f,
[28a]
[28b]
[10a]
[10a]
[31]
[32]
[11a]
1
0g,
10h,
11,
12,
13a, 13b, 14,
and 15
are identical to those published in the literature.
Figure 5. Recycling of the Pd(OAc) /m-TPPTC system in an
2
General Experimental Procedure for Sonogashira
Reactions
H O/C H CN system.
2
3
7
PdL was preformed in water (30 mL/mmol Pd) by mixing
2
1
8
mol % of palladium acetate and 4 mol % of m-TPPTC at
08C during 30 minutes. To the red-colored catalyst was added
Conclusion
an acetonitrile (2 mL/mmol) solution of the substrate and the
base (2.5 equivs.). The homogeneous mixture was stirred at
The steric and electronic features of the novel water-
soluble phosphane m-TPPTC have been determined
and compared to the well-known sulfonated analogue
TPPTS. We have shown through several methods in-
cluding NMR, IR and UV-VIS spectroscopy, that the
m-TPPTC phosphane is more basic than the sulfonated
6
08C until completion of the reaction (GC), cooled to room
temperature, then filtered on a short pad of florisil gel and
evaporated under reduced pressure. The residue was purified
by silica gel chromatography if needed.
1
4-(2-Aminophenyl)-2-methylbut-3-yn-2-ol (10b): H NMR
TPPTS ligand. Various copper-free Pd-catalyzed Sono- (CDCl , 250 MHz): d¼7.16 (dd, 1H, J¼1.8, 7.8 Hz), 7.02 (td,
3
gashira cross-couplings on aryl iodides and ortho-func- 1H, J¼1.8, 7.8 Hz), 6.60 (dd, 1H, J¼1.3, 7.8 Hz), 6.56 (td,
1
H, J¼1.3, 7.8 Hz), 4.10 (brs, 2H), 2.90 (brs, 1H), 1.54 (s,
13
tionalized aryl iodides were efficiently performed using
the carboxylated phosphane m-TPPTC. This phosphane
induced a different selectivity compared to its sulfonat-
ed analogue, which may be explained by the difference
of basicity between both ligands. Moreover, further
studies in the rhodium-catalyzed arylation reactions
provided similar differences in terms of selectivity and
6
H); C NMR (CDCl , 63 MHz): d¼148.1 (C ar.), 132.5
3
q
(
(
(
CH ar.), 130.0 (CH ar.), 118.4 (CH ar.), 114.9 (CH ar.), 108.0
C ar.), 100.0 (C ), 79.0 (C ), 66.1 (C ), 32.1 (2 CH ); GC
708C/1 min then 208C min to 2108C): RT¼9.0; mp 558C.
q
q
q
1
q
3
ꢀ
N-[2-(4-Bromophenylethynyl)-phenyl]acetamide
(10d):
1
H NMR (DMSO, 200 MHz): d¼9.53 (brs, 1H), 7.77 (d, 1H,
J¼7.8 Hz), 7.67 (d, 2H, J¼8.4 Hz), 7.66 (d, 1H, J¼7.8 Hz),
efficiency between the water-soluble ligands. We also 7.56 (d, 2H, J¼8.4 Hz), 7.40 (t, 1H, J¼7.8 Hz), 7.18 (t, 1H,
1
3
performed highly efficient recycling of the Pd/m- J¼7.8 Hz), 2.13 (s, 3H); C NMR (DMSO, 100 MHz): d¼
TPPTC system under mild conditions in the Sonoga- 168.8 (C ), 139.4 (C ar.), 133.6 (2 CH ar.), 132.3 (CH ar.),
32.0 (2 CH ar.), 129.6 (CH ar.), 124.7 (CH ar.), 124.0 (CH
ar.), 122.4 (C ar.), 121.9 (C ar.), 115.4 (C ar.), 93.7 (C ),
q
q
1
shira reaction. Further applications of other metal/m-
TPPTC systems are currently under investigation in
our laboratory and will be reported in due course.
q
q
q
q
8
7.4 (C ), 23.8 (CH ); mp 1958C.
q 3
4
-(2-Amino-5-trifluoromethylphenyl)-2-methylbut-3-yn-2-
1
ol (10i): H NMR (CDCl , 200 MHz): d¼7.51 (s, 1H), 7.33 (d,
3
1
H, J¼8.5 Hz), 6.71 (d, 1H, J¼8.5 Hz), 4.51 (brs, 2H), 2.31
1
3
(
(
(
3
brs, 1H), 1.65 (s, 6H); C NMR (CDCl , 50 MHz): d¼150.1
3
Experimental Section
C ar.), 129.4 (CH ar.), 126.4 (CH ar.), 120.6 (C ar.), 118.7
q
q
CF ), 113.6 (CH ar.), 106.8 (C , C ar.), 100.3 (C ), 65.7 (C ),
3
q
q
q
1
q
ꢀ
1.5 (2 CH ); GC (708C/1 min then 208C min to 2108C):
3
General Remarks
þ
RT ¼5.2; mp 1188C; GC/MS (EI): m/z¼243 (M) ; anal. calcd.
1
13
H NMR and C NMR spectra were recorded on a Bruker AC
00, AV 250 or ARX 400 instrument. All signals are expressed
as (d) ppm downfield from Me Si used as an internal standard
for C H F NO: C 59.26, H 4.97, N 5.76; found: C 60.08, H 5.06,
1
2
12 3
2
N 5.60.
Methyl [4-Amino-3-(3-hydroxy-3-methylbut-1-ynyl)]ben-
4
1
13
1
for H and C NMR. Coupling constants (J) are reported in Hz
and refer to apparent peak multiplicities. GC analyses were
performed with a Hewlett-Packard 5890 instrument equipped
with a J&W Scientific DB-1701 capillary column (15 m, d
zoate (10j): H NMR (CDCl , 200 MHz): d¼1.65 (s, 6H),
3
2.27 (brs, 1H), 3.88 (s, 3H), 4.61 (brs, 2H), 6.66 (d, 1H, J¼
8.5 Hz), 7.79 (dd, 1H, J¼2, 8.5 Hz), 7.97 (d, 1H, J¼2 Hz);
1
3
C NMR (CDCl , 50 MHz): d¼166.5 (C ), 151.4 (C ar.),
3
q
q
0
.254 mm), using a flame ionization detector. Elemental analy-
ses were performed at the University of Pierre et Marie Curie
UPMC Paris VI). Mass spectrometric analyses were per-
134.1 (CH ar.), 131.1 (CH ar.), 118.6 (C ar.), 113.0 (CH ar.),
106.3 (C ar.), 99.7 (C ), 77.3 (C ), 65.4 (C ), 51.5 (CH ), 31.3
(2 CH ); GC (708C/1 min then 208C min to 2108C): RT¼
q
q
q
q
q
ꢀ
3
1
(
3
Adv. Synth. Catal. 2004, 346, 1733–1741
asc.wiley-vch.de
ꢀ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1739

FULL PAPERS
Emilie Genin et al.
þ
8
.7; mp 1288C; GC/MS (EI): m/z¼233 (M) ; anal. calcd. for
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C H NO : C 66.94, H 6.48, N, 6.00; found: C 66.36, H 6.74,
13
15
3
N, 6.07.
2
2
25; b) W. Chen, L. Xu, J. Xiao, Org. Lett. 2000, 2,
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Acknowledgements
R. A. is grateful to the Minist e` re de lꢀEducation et de la Recher-
che for a grant (1999–2002). E. G. is thankful to the Ecole Nor-
male Sup e´ rieure de Paris for a grant (2003–2004).
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