Biphasic aqueous organometallic catalysis promoted by cyclodextrins: How to design the water-soluble phenylphosphane to avoid interaction with cyclodextrin

Article abstract of DOI:10.1002/adsc.200700582

The ability of cyclodextrin to interact with meta-trisulfonated triphenylphosphane derivatives bearing one or two methyl (or methoxy) groups on the aromatic ring has been investigated by NMR and UV-vis spectroscopy. In the case of native β-cyclodextrin (β-CD), the presence of one methyl or methoxy group in the ortho-position on each aromatic ring is necessary to hamper the formation of an inclusion complex between the β-CD and meta-trisulfonated triphenylphosphane derivatives. In the case of methylated β-CD, the formation of an inclusion complex is only observed when the meta-trisulfonated triphenylphosphane contains a methyl group in the para-position. The poor affinity of methylated β-CD towards modified trisulfonated triphenylphosphanes was attributed to the steric hindrance generated by the methyl groups on the CD secondary face. The absence or presence of an interaction between phosphanes and methylated β-CD was also confirmed by catalytic experiments. Thus, the phosphanes that do not interact with the methylated CD were the most efficient mass-transfer promoters in an aqueous biphasic palladium-catalyzed Tsuji-Trost reaction.

Full text of DOI:10.1002/adsc.200700582

UPDATES
DOI: 10.1002/adsc.200700582
Biphasic Aqueous Organometallic Catalysis Promoted by
Cyclodextrins: How to Design the Water-Soluble
Phenylphosphane to Avoid Interaction with Cyclodextrin
Michel Ferreira,a HervØ Bricout,a Adlane Sayede,a Anne Ponchel,a
Sophie Fourmentin,b SØbastien Tilloy,a and Eric Monfliera,*
a
UniversitØ d’Artois, UnitØ de Catalyse et de Chimie du Solide (UCCS), UMR CNRS 8181, Groupe Catalyse
SupramolØculaire et Chimie de CO, Rue Jean Souvraz, SP 18, 62307 Lens CØdex, France
Fax : (+33)-3-2179-1755; e-mail: monflier@univ-artois.fr
UniversitØ du Littoral, Laboratoire de Synth›se Organique et Environnement, 145 avenue Maurice Schumann, 59140
b
Dunkerque, France
Fax : (+33)-3-2823-7605
Received: October 12, 2007; Revised: January 10, 2008; Published online: February 25, 2008
Supporting information for this article is available on the WWW under http://asc.wiley-vch.de/home/.
Abstract: The ability of cyclodextrin to interact
with meta-trisulfonated triphenylphosphane deriva-
tives bearing one or two methyl (or methoxy)
groups on the aromatic ring has been investigated
by NMR and UV-vis spectroscopy. In the case of
native b-cyclodextrin (b-CD), the presence of one
methyl or methoxy group in the ortho-position on
each aromatic ring is necessary to hamper the for-
mation of an inclusion complex between the b-CD
and meta-trisulfonated triphenylphosphane deriva-
tives. In the case of methylated b-CD, the formation
of an inclusion complex is only observed when the
meta-trisulfonated triphenylphosphane contains a
methyl group in the para-position. The poor affinity
of methylated b-CD towards modified trisulfonated
triphenylphosphanes was attributed to the steric
hindrance generated by the methyl groups on the
CD secondary face. The absence or presence of an
interaction between phosphanes and methylated b-
CD was also confirmed by catalytic experiments.
Thus, the phosphanes that do not interact with the
methylated CD were the most efficient mass-trans-
fer promoters in an aqueous biphasic palladium-cat-
alyzed Tsuji–Trost reaction.
chemicals due to the low cost and toxicity of water.
Furthermore, the catalyst that is immobilized into the
aqueous phase by water-soluble ligands can be easily
recovered by simple separation of the aqueous and
organic phases.[1] The most commonly used water-
soluble ligand is the sodium salt of meta-trisulfonated
triphenylphosphane [TPPTS;
P(m-C6H4SO3Na)3]
which was originally developed by Rhone-Poulenc for
use in the aqueous-phase hydroformylation of propyl-
ene.[2] Although appropriate for water-soluble sub-
strates, the aqueous organometallic catalysis suffered
from a huge loss of attractiveness when hydrophobic
substrates were considered because of mass-transfer
limitations.[3]
Cyclodextrins (CDs) have been widely used in
aqueous organometallic catalysis to overcome mass-
transfer limitations. Indeed, CDs can improve the
mass transport across the interface by forming inclu-
sion complexes with highly hydrophobic substrates.[4]
Among the different CDs used, the randomly methy-
lated b-CD (Rame-b-CD) appeared to be the most ef-
ficient (Table 1).[5]
Indeed, Rame-b-CD notably increased the reaction
rates, while avoiding the formation of an emulsion
and the partition of the catalyst between the organic
and aqueous phases. Nevertheless, this b-CD deriva-
tive forms an inclusion complex with the TPPTS
ligand.[6] The formation of such inclusion complexes
induces a decrease in the linear to branched aldehyde
ratio during the rhodium-catalyzed hydroformylation
reaction.[7] In fact, the Rame-b-CD is able to dissoci-
ate TPPTS from the rhodium species and leads to the
formation of low-coordinated phosphane species re-
Keywords: aqueous phase catalysis; cyclodextrin;
phosphanes; supramolecular chemistry
Introduction
Aqueous organometallic catalysis appears to be an sponsible for this decrease in regioselectivity. In addi-
environmentally friendly method to produce organic tion, it has been shown that the ability of Rame-b-CD
Adv. Synth. Catal. 2008, 350, 609 – 618
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Michel Ferreira et al.
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Table 1. Structure of CD and Rame-b-CD.
Abbreviation
n
Substituent (G)
Carbon bearing the OCH3 group
Average number of OCH3 group by CD
b-CD
Rame-b-CD
7
7
H
CH3
(À)
0
12.6
2, 3 and 6
to bind to the TPPTS ligand can contribute to de- Results and Discussion
crease the reaction rates. Indeed, when the TPPTS/
Rame-b-CD ratio is too high, the CD cavity is pois- Synthesis of the Water-Soluble Phosphanes
oned by the ligand and the substrate transfer is dimin-
ished.[8] As approaches based on the use of a-CD de- The various water-soluble phosphanes were synthe-
rivatives[9] or chemically modified b-CD[10,11] have not sized according to procedures described in the litera-
given full satisfaction to solve the above problems, ture. Briefly, the methylated or methoxylated deriva-
strategies based on phosphane modification are now tive of the triphenylphosphane was dissolved in a mix-
explored.[12]
ture sulfuric acid/oleum for sulfonation. After hydrol-
In this work, we examined the potential of bulky ysis of SO3, trioctylamine was added to extract the re-
TPPTS derivatives in aqueous organometallic cataly- action product. Finally, the sodium salt was obtained
sis promoted by CD. As tri- or tetrasubstituted aro- by addition of NaOH (Scheme 1).
matic rings are largely less associated with CDs than
The purity of these water-soluble phosphanes was
mono- or disubstituted ones, it was expected that at- carefully controlled. In particular, 1H and 31P{1H}
tachment of substituents groups on the aromatic ring NMR analysis indicated that for each phosphane only
of the TPPTS would be sufficient to hamper the for- less than 5% of its oxide was present.
mation of an inclusion complex between b-CD and
the phosphane.[13] So, we have synthesized TPPTS de-
rivatives bearing one or two methyl (or methoxy) Studies of b-CD/Phosphane Interactions
groups on each aromatic ring and investigated by
NMR and UV-vis spectroscopy the influence of the NMR and UV-vis spectroscopic studies have been
group position and/or the group number on the inclu- performed to provide information concerning the po-
sion phenomenon. Finally, the behavior of these phos- tential interactions between these water-soluble phos-
phanes in a model reaction has been examined to phanes and b-CD in aqueous medium. When an inter-
confirm the presence or absence of interactions be- action was evidenced, the stoichiometry and the asso-
tween the phosphanes and cyclodextrins.
The water-soluble phosphanes used in this work are ments were also performed to determine whether the
schematically presented in the Table 2. phosphane is deeply included into the b-CD cavity.
It should be noticed that tris(p-Me)TPPTS, tris- The main results are gathered in Table 2. For compar-
(m,p-diMe)TPPTS, bis(o-Me)TPPTS and tris(o- ison, the data concerning the inclusion complex be-
Me)TPPDS have never been described in the litera- tween b-CD and TPPTS are also indicated.
ture, in contrast to tris (o- Our first studies were devoted to TPPTS deriva-
(o,p-diMe)TPPTS[14], tris
Me)TPPTS[15] (p-OMe)TPPTS[16] and tris
tris (o- tives bearing a methyl or a methoxy group in a para
OMe)TPPTS.[15] Interestingly, some catalysts based on position [tris
(p-Me)TPPTS or tris(p-OMe)TPPTS, re-
these ligands have given interesting results in aqueous spectively]. As an illustrative experiment, the case of
organometallic catalysis. Hence, tris(o,p-diMe)TPPTS b-CD and tris(p-Me)TPPTS is fully described. For
and tris
ciation constant were determined. T-ROESY experi-
AHCTREUNG
A
N
ACHTREUNG
A
ACHTREUNG
,
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
(p-Me)TPPTS and b-CD, the 31P{1H}
ACHTREUNG(o-Me)TPPTS provided active catalysts in the mixtures of trisCAHTREUGN
1
hydrogenation of aldehydes,[17] Heck and Suzuki cou- and H NMR spectra exhibited chemical shift varia-
plings of aryl bromide[18] or Suzuki couplings of un- tions compared to the spectra of these two com-
protected halonucleosides.[19] In addition, tris
ACHTREUNG
AHCTREUNG
ACHTREUNG(o-OMe)TPPTS during the hydroformylation reac- trations using the continuous variation technique
tion.[21]
(Jobꢁs method – see Supporting Information).[22] The
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Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins
UPDATES
Table 2. Structure and abbreviation of the water-soluble phosphanes. Values of association constant[a] (K) and presence of
cross peaks in T-ROESY spectra for the b-CD/phosphane couple.
Structure
Name, Abbreviation
K
T-ROESY
(MÀ1) cross peaks[c]
tris(3-sulfonatophenyl)phosphane sodium salt, TPPTS
1200 Yes
tris(4-methyl-3-sulfonatophenyl)phosphane sodium salt, trisACTHRE(UNG p-
Me)TPPTS
2750 Yes
tris(4-methoxy-3-sulfonatophenyl)phosphane sodium salt, tris
OMe)TPPTS
ACHTRE(UNG p-
400
140
Yes
No
tris(4,5-dimethyl-3-sulfonatophenyl)phosphane sodium salt, trisACHTER(UNG m,p-
diMe)TPPTS
tris(4,6-dimethyl-3-sulfonatophenyl)phosphane sodium salt, trisACHTER(UNG o,p-
diMe)TPPTS
(À)[b] No
tris(6-methyl-3-sulfonatophenyl)phosphane sodium salt, trisACTHRE(UNG o-
Me)TPPTS
(À)[b] No
tris(6-methoxy-3-sulfonatophenyl)phosphane sodium salt, trisACTHRE(UNG o-
OMe)TPPTS
(À)[b] No
bis(6-methyl-3-sulfonatophenyl)(3-sulfonatophenyl)phosphane sodium
salt, bisACHTER(UNG o-Me)TPPTS
110
50
No
No
bis(6-methyl-3-sulfonatophenyl)(2-methylphenyl)phosphane sodium
salt, tris(o-Me)TPPDS
AHCTREUNG
[a]
When an interaction between the phosphane and b-CD was observed, the stoichiometry of the adduct or inclusion com-
plex has been determined to be equal to 1:1.
No inclusion complex was evidenced.
The term Yes is used when marked cross-peaks between protons of the water-soluble phosphane and b-CD were observed
in the T-ROESY spectra at 298 K.
[b]
[c]
Jobꢁs plot shows a maximum at r=0.5 and a highly It must be pointed out that this value is higher than
symmetrical shape, indicating that the stoichiometry that found for the b-CD/TPPTS complex (K=
of inclusion complex is 1:1. The association constant 1200MÀ1). This result was clearly unexpected as the
was evaluated at 298 K from UV-Vis spectroscopic introduction of a methyl group was initially thought
data (spectral displacement method – see Supporting to decrease the affinity of the phosphane for the CD!
Information) and was found to be equal to 2750MÀ1. The structure of the b-CD/tris
ACHTRE(UNG p-Me)TPPTS inclusion
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Michel Ferreira et al.
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complex was elucidated by a two-dimensional T-
ROESY NMR experiment (Figure 1).
The strongest interactions are observed between
the internal protons of the b-CD (H-3 and H-5) and
the three aromatic protons of tris
ACHTREUNG
addition, the protons of the methyl groups of trisACHTREUNG
Me)TPPTS are correlated with the H-3, H-5 and H-6
protons. Interestingly, the absence of an interaction
between the H-6 protons of b-CD and the aromatic
protons of trisCAHTRE(UNG p-Me)TPPTS indicates clearly that the
inclusion occurs by the secondary face of b-CD.
By using the same methodology, the association
constant for the 1:1 inclusion complex between the b-
CD/tris
400MÀ1. Contrary to tris
tion of a methoxy group clearly decreases the affinity
of the phosphane for b-CD. The tris(p-OMe)TPPTS is
probably more encumbered than tris(p-Me)TPPTS,
ACHTREUNG
AHCTREUNG
AHCTREUNG
AHCTREUNG
and a deep penetration inside the b-CD cavity is
likely more difficult. This assumption was supported
by T-ROESY experiments. Indeed, the absence of in-
teraction between the H-5 proton of the b-CD and
the protons of the phosphane in the T-ROESY spec-
tra indicate clearly a shallow inclusion (see Support-
ing Information).
Scheme 1. General procedure for the synthesis of the water-
soluble phosphanes.
Figure 1. Partial contour plot of the T-ROESY spectrum of a solution containing b-CD (10 mM) and tris
(10 mM) in D2O at 298 K with a 300 ms mixing time. The interactions observed in the T-ROESY spectrum are indicated by
arrows. The deduced orientation of tris(p-Me)TPPTS in b-CD cavity is shown.
ACHTRE(UGN p-Me)TPPTS
AHCTREUNG
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Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins
UPDATES
From the above results, it appears that the presence
From these experimental data, it appears that the
of one methyl or methoxy group in the para position formation of an inclusion complex between b-CD and
on each aromatic ring of the TPPTS is not sufficient a TPPTS derivative can be avoided by introducing a
to prevent the formation of an inclusion complex with substituent on each ring in the ortho position of the
b-CD. In these conditions, we decided to introduce phosphane. In the next part, the behavior of the
two methyl groups on each aromatic cycle in the TPPTS derivatives towards Rame-b-CD was investi-
para/meta positions [tris
ACHTREUNG
para/ortho positions [trisAHCTREUNG
ciation constant of the 1:1 complex b-CD/trisACTHRE(UNG m,p-di-
Me)TPPTS was evaluated as 140MÀ1 that is synony-
mous of a weakly associated inclusion complex. For Studies of Rame-b-CD/Phosphane Interactions
the b-CD/trisACHTREUNG(o,p-diMe)TPPTS mixture, no spectral
modification was observed during NMR or UV-vis ex- In the case of Rame-b-CD, inclusion of the phos-
periments, indicating that this phosphane did not in- phane into the CD cavity is clearly more difficult.
teract with b-CD. These results were also confirmed Indeed, NMR and UV-vis spectroscopic studies indi-
by T-ROESY experiments. In the two cases, no cate that Rame-b-CD interacts only with TPPTS and
marked cross-peaks between the b-CD and phos- trisACTHRE(UNG p-Me)TPPTS phosphanes. The 1:1 association
phane protons have been observed on the T-ROESY constant values were evaluated as 840MÀ1 and
spectrum, proving a not very deep or an absence of 960MÀ1 for Rame-b-CD/TPPTS and Rame-b-CD/tris-
an inclusion phenomenon. Consequently, it can be
ACHTRE(UNG p-Me)TPPTS inclusion complexes, respectively. It
concluded that the presence of two methyl groups in must also be pointed that these values are lower than
meta/para or in ortho/para positions on each aromatic those observed with native b-CD. This decrease is
ring blocks the penetration inside the b-CD cavity largely more marked in the case of trisACHTREUNG
with a more pronounced effect in the case of tris
diMe)TPPTS.
ACHTREUNG
The importance of methyl groups in the ortho posi- 840MÀ1 with Rame-b-CD).
tion was demonstrated by NMR and UV-vis spectros-
These results demonstrate that the inclusion capaci-
(o- ty of b-CD is markedly altered by introduction of
Me)TPPTS. Indeed, no interaction between trisACHTRE(UGN o- methyl groups. The steric hindrance generated by the
copy experiments on mixtures of b-CD and trisACHTREUNG
Me)TPPTS and b-CD can be evidenced. The same ex- methyl groups on the CD secondary face impedes in-
periments performed with tris(o-OMe)TPPTS and b- clusion of the more encumbered water-soluble phos-
AHCTREUNG
CD have equally concluded to the absence of interac- phanes. These results are in line with those obtained
tions. The methylation or methoxylation in the ortho with the native b-CD. Indeed, it has been observed
position for each aromatic ring is therefore sufficient with the native b-CD that most of the phosphanes
to generate a constraint preventing the penetration of were not deeply included in the cavity suggesting that
these water-soluble phosphanes inside the b-CD a supplementary steric constraint would suppress the
cavity.
inclusion. This result is very promising as the Rame-
To determine the required number of methyl group b-CD is the most efficient mass transfer agent in
in the ortho positions to prevent the inclusion process, aqueous organometallic catalysis. So, except for
the behavior of a TPPTS bearing a methyl group in TPPTS and tris
ACHTRE(UGN p-Me)TPPTS, the other phosphanes
the ortho position on only two aromatic rings [bis(o- should be valuable ligands for aqueous organometal-
AHCTREUNG
Me)TPPTS] was examined. This phosphane was lic catalysis promoted by methylated b-CDs. Some ex-
found to weakly interact with b-CD as the association periments in catalysis have been performed to support
constant was equal to 110MÀ1 and no cross-peak cor- this assumption.
relation was observed on the T-ROESY spectrum.
This result undoubtedly demonstrates that the pres-
ence of three methyl groups is necessary to obtain a Catalytic Experiments
non-interacting phosphane. However, it must be
pointed out that the sulfonato group contributes also The removal of the allyloxycarbonyl group from an
to impede the formation of inclusion complex. allylic carbonate (allyl undecyl carbonate) was chosen
Indeed, we have found that a meta-disulfonated tri- as the model reaction to evaluate the behavior of
phenylphosphane bearing a methyl group in the ortho water-soluble phosphanes in the presence of Rame-b-
position on each aromatic ring [trisACHTER(UNG o-Me)TPPDS in- CD (Figure 2). This reaction was catalyzed by a palla-
teracts with the b-CD (K=50MÀ1)]. However, this in- dium/water-soluble phosphane combination in the
teraction does not lead to the formation of a genuine presence of diethylamine as allyl scavenger.[23]
inclusion complex as no cross-peak has been observed
on the T-ROESY NMR spectrum.
The presence or absence of an interaction between
the phosphane and Rame-b-CD can be easily detect-
Adv. Synth. Catal. 2008, 350, 609 – 618
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Michel Ferreira et al.
UPDATES
Figure 2. Influence of the Rame-b-CD/phosphane ratio on the reaction rate for different water-soluble phosphanes.
ed by examining the effect of increasing amounts of Me)TPPTS, tris
A
ACHTREUNG
Rame-b-CD on the reaction rate. In fact, the reaction Me)TPPTS, respectively. In the case of trisACHTREUNG
rate linearly increases with the Rame-b-CD concen- Me)TPPDS, the reaction rate was higher than those
tration when no interaction occurs between the phos- observed with the other phosphanes and was equal to
phane and Rame-b-CD.[8] In contrast, when the phos- 803 mmol/h. This higher activity is likely connected
phane interacts with the Rame-b-CD, Rame-b-CD is with the more pronounced hydrophobic character of
trapped by the phosphane ligand and is unable to par- this phosphane. Indeed, compared to the other
ticipate in the mass-transfer process at low CD/phos- TPPTS derivatives, the trisACHTER(UNG o-Me)TPPDS phosphane
phane ratios (excess of ligand relative to CD). In contains only two sulfonate groups. Consequently, this
these conditions, a significant rate increase can only phosphane is preferentially situated at the interface
be observed at high CD/phosphane ratios when the facilitating the contact between the catalyst and the
amounts of CD are higher than those of ligand (i.e., substrate.[24]
for a CD/ligand ratio> 1). The results obtained in the
presence of various amounts of Rame-b-CD are the addition of Rame-b-CD increases the reaction
shown in Figure 2. rates (Figure 2). However, effect of the Rame-b-CD
As expected for a mass-transfer limited reaction,
Before examining the effect of Rame-b-CD on the on the reaction rate depends on the phosphane. In
reaction rate, it should be pointed out that the activity fact, the plot of reaction rate vs. Rame-b-CD/phos-
of the catalytic system in the absence of Rame-b-CD phane ratio is linear for tris
A
ACHTREUNG
strongly depends on the phosphane (Figure 2 – diMe)TPPTS,
tris
A
ACHTREUNG
[Rame-b-CD]/[Phosphane]=0). Concerning the dif- Me)TPPDS, tris
A
ACHTREUNG
ferent TPPTS derivatives, the activities are low as the and tris
reaction rates were equal to 2, 2, 7, 11, 35, 46 and 81 TPPTS and tris
mmol/h for tris(o-OMe)TPPTS, tris(p-OMe)TPPTS, ly in agreement with our spectroscopic studies.
(o-Me)TPPTS, tris(p-Me)TPPTS, tris(o- Indeed, the shape of the curves appears directly relat-
ACHTREUNG
AHCTREUNG
A
ACHTREUNG
bis
N
G
ACHTREUNG
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Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins
UPDATES
Acros in their highest purity and used without further purifi-
cation. Rame-b-CD was purchased from Aldrich Chemicals.
This CD was partially methylated. Methylation occurred at
positions 2, 3, or 6 and 1.8 OH groups per glucopyranose
unit were statistically modified. Distilled deionized water
was used in all experiments. All solvents and liquid reagents
were degassed by bubbling N2 for 15 min before each use or
by two freeze-pump-thaw cycles before use.
ed to the nature of interaction between Rame-b-CD
and the phosphane. The reaction rate linearly increas-
es when the water-soluble phosphanes do not interact
with Rame-b-CD as expected for a non-interacting
system. In contrast, the reaction rate significantly in-
creases when the CD/phosphane ratio is higher than 1
in the case of the TPPTS and trisACHTRE(UNG p-Me)TPPTS, con-
firming the interaction of these two phosphanes with
the Rame-b-CD.
Preparation of Water-Soluble Phosphanes
TPPTS,[25] tris
tris
(o-OMe)TPPTS[15] were prepared as reported in the liter-
ature. Tris(o,p-diMe)TPPTS was obtained from Strem. The
(o-Me)TPPTS,[15] tris(p-OMe)TPPTS[16] and
ACHRTEUNG ACHTREUGN
AHCTREUNG
Conclusions
AHCTREUNG
purity of these water-soluble phosphanes was controlled by
1H, 13C and 31P{1H} NMR analysis and MALDI-TOF. For
the other water-soluble phosphanes, the procedures are de-
scribed in the following. The full 1H, 13C{1H} and 31P{1H}
We have demonstrated by spectroscopic studies and
catalysis experiments that bulky TPPTS derivatives
can be valuable water-soluble phosphanes for aqueous
organometallic catalysis promoted by modified cyclo-
dextrins. Indeed, each compound can fully play its
own role without mutual interaction: the water-solu-
ble bulky phosphane as a ligand for the metal and the
CD as an efficient mass transfer promoter.
spectra of tris
G
G
ACHTREUNG(o-
Me)TPPTS and tris
ing Information.
ACHTREUNG
Trisodium Salt of Tris(4,5-dimethyl-3-
sulfonatophenyl)phosphane [tris
(Scheme 2)
ACHTRE(UNG m,p-diMe)TPPTS]
Experimental Section
To a suspension of magnesium (10 g, 0.41 mol, 1.2 equiv.) in
60 mL of anhydrous THF was introduced under nitrogen
the iodide derivative (27 g, 0.116 mol, 0.33 equiv.). After a
few minutes, the reaction began and 55 g (0.235 mol, 0.66
equiv.) of the iodide derivative in THF (240 mL) were
added dropwise. The reaction mixture was then heated
under reflux for 1 hour. After cooling, phosphorus trichlor-
ide (16 g, 0.117 mol, 0.33 equiv.) in THF (50 mL) was added
dropwise and then heated under reflux for 1 hour. Once the
reaction was complete, the mixture was poured into a mix-
ture of ice (100 g) and water (100 mL). The organic phase
was washed with water (3”50 mL), dried over anhydrous
MgSO4, filtered and concentrated by rotary evaporation.
Yield: 21%.
The resulting oil (8.51 g) was then dissolved in 45 mL of
100% concentrated sulfuric acid obtained by mixture of
36 mL of concentrated sulfuric acid (96%) and 9 mL of
oleum (65%). After cooling to 58C, the oleum (65%,
10.5 mL) was added slowly under vigorous stirring and
keeping the temperature below 108C. The reaction mixture
was then kept at room temperature for 10 h under a nitro-
gen atmosphere. Excess of SO3 was transformed to H2SO4
by addition of 10 mL of degassed water (Caution!). The
mixture was poured into a mixture of water and ice
(250 mL/250 g), and trioctylamine (27 g, 75.6 mmol) was
then added. The ammonium salt of the sulfonated phos-
phane was recovered from the acidic aqueous layer by addi-
General Remarks
1
The H, 13C and 31P NMR spectra were recorded at 300.13,
75.47 and 121.49 MHz on a Bruker Avance DRX spectrom-
eter, respectively. Mass spectra were recorded on a MALDI
TOF TOF Bruker Daltonics Ultraflex II. The 2D T-ROESY
experiments were run using the software supplied by
Bruker. T-ROESY experiments were preferred to classical
ROESY experiments as this sequence provides reliable di-
polar cross-peaks with a minimal contribution of scalar
transfer. Mixing times for T-ROESY experiments were set
at 300 ms. The data matrix for the T-ROESY was made of
512 free induction decays, 1 K points each, resulting from
the co-addition of 32 scans. The real resolution was 1.5–
6.0 Hz/point in F2 and F1 dimensions, respectively. They
were transformed in the non-phase-sensitive mode after
QSINE window processing. UV-vis spectroscopy was per-
formed on a Perkin–Elmer Lamba 2S spectrometer. The cell
used was placed in a cuvette holder and the temperature
was kept constant at 298Æ0.1 K by means of a thermostated
bath. Gas chromatographic analyses were carried out on a
Shimadzu GC-17A gas chromatograph equipped with a
methyl silicone capillary column (30 m”0.32 mm) and a
flame ionization detector (GC:FID).
D2O (99.95% isotopic purity) was obtained from Merck.
All reactants were purchased from Aldrich Chemicals or
Scheme 2. Synthesis of [trisCAHTRE(UNG m,p-diMe)TPPTS].
Adv. Synth. Catal. 2008, 350, 609 – 618
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asc.wiley-vch.de
615

Michel Ferreira et al.
UPDATES
tion of chloroform (3”30 mL) and the organic layer was
washed with water up to neutral pH. The sulfonated salt
was recovered by a succession of extractions with NaOH so-
lution (2N). Each fraction was analyzed by 31P{1H} NMR
spectroscopy and the fractions where a unique signal was
observed were concentrated under vacuum and a white
solid was obtained. Yield: 7%. 1H NMR (300 MHz, D2O,
258C): d=2.23 (s, 9H, H-4), 2.49 (s, 9H, H-6), 7.20 (d,
3JP, H =7.8 Hz, 3H, H-2), 7.66 (d, 3JP, H =8.10 Hz, 3H, H-8);
13C-{1H} NMR (75.5 MHz, D2O, 25 8C): d=16.24 (s, C-6),
19.86 (s, C-4), 129.88 (d, 2JP, C =23.4 Hz, C-8), 132.93 (d,
ture was poured into a mixture of ice (100 g) and water
(100 mL). The organic phase was washed with water (3”
50 mL), dried over anhydrous MgSO4, filtered and concen-
trated by rotary evaporation. The resulting oil was recrystal-
lized from methanol to give white crystals. Yield: 25%.
The resulting product (7.08 g) was then dissolved in
17.9 mL of 100% concentrated sulfuric acid obtained by
mixture of 14.3 mL of concentrated sulfuric acid (96%) and
3.6 mL of oleum (65%). After cooling to 58C, the oleum
(65%, 19.8 mL) was added slowly under vigorous stirring
and keeping the temperature below 108C. The reaction mix-
ture was then kept at room temperature for 72 h under a ni-
trogen atmosphere. Excess of SO3 was transformed to
H2SO4 by addition of 10 mL of degassed water (Caution!).
The mixture was poured into a mixture of water and ice
(250 mL/250 g), and trioctylamine (26.4 g, 74.6 mmol) was
then added. The ammonium salt of the sulfonated phos-
phane was recovered from the acidic aqueous layer by addi-
tion of chloroform (3”30 mL) and the organic layer was
washed with water up to neutral pH. The sulfonated salt
was recovered by a succession of extractions with a NaOH
solution (2N). Each fraction was analyzed by 31P{1H} NMR
spectroscopy and the fractions where a unique signal was
observed were concentrated under vacuum and a white
2
3JP, C =7.5 Hz, C-3), 136.81 (s, C-5), 137.62 (d, JP, C =16.6 Hz,
1
3
C-2), 140.75 (d, JP,C =6.0 Hz, C-1), 141.83 (d, JP, C =7.5 Hz,
C-7); 31P-{1H} NMR (121.5 MHz, D2O, 25 8C): d=À7.38 (s);
MS (MALDI-TOF): m/z=1327.21 [2P+Na]+, 1305.22 [2P+
H]+, 675.10 [P+Na]+, 653.12 [P+H]+; elemental analysis
calcd. (%) for C24H24Na3O9PS3·3H2O (706.6): C 40.79, H
4.28; found: C 40.65, H 4.20.
Trisodium Salt of Tris(4-methyl-3-
sulfonatophenyl)phosphane [trisACHTRE(UGN p-Me)TPPTS]
The procedure described above
was used for the sulfonation of tris-
AHCTREUNG
(p-Me)TPP. Yield: 45%. 1H NMR
1
solid was obtained. Yield: 21%. H NMR (300 MHz, D2O,
258C): d=2.27 (s, 6H, H-3), 7.01 (dd, 3JP, H =4.2 Hz,
4JH-5,H-7 =1.7 Hz, 2H, H-7), 7.27 (t, 3JP, H =3JH-9,H-10 =7.0 Hz,
(300 MHz, D2O, 25 8C): d=2.52 (s,
9H, H-5), 7.13 (t, 3JP, H =3JH-2,H-3
=
=
=
3
4
3
7.2 Hz, 3H, H-2), 7.21 (d, JH,H
1H, H-9), 7.36 (dd, JP, H =4.6 Hz, JH-4,H-5 =8.1 Hz, 2H, H-4),
3
7.47 (t, 3JH-10,H-11 =3JH-9,H-10 =7.7 Hz, 1H, H-10), 7.62 (dd,
7.2 Hz, 3H, H-3), 7.73 (d, JP, H
8.4 Hz, 3H, H-7); 13C-{1H} NMR (75.5 MHz, D2O, 25 8C):
3JH-4,H-5 =8.1 Hz, 4JH-5,H-7 =1.7 Hz, 2H, H-5), 7.76 (d, JP, H
=
3
2
9.1 Hz, 1H, H-13), 7.77 (d, 3JH-11,H-10 =7.7 Hz, 1H, H-11);
d=19.82 (s, C-5), 131.99 (d, JP, C =24.1 Hz, C-7), 133.12 (d,
3JP, C =6 Hz, C-3), 133.58 (d, 1JP, C =8.3 Hz, C-1), 136.48 (d,
13C-{1H} NMR (75.5 MHz, D2O, 25 8C): d=20.6 (d, JP, C
=
3
3
2JP, C =16.6 Hz, C-2), 138.26 (s, C-4), 141.63 (d, JP, C =7.5 Hz,
19.8 Hz, C-3), 126.79 (s, C-5), 127.32 (s, C-11), 129.66 (s, C-
C-6); 31P-{1H} NMR (121.5 MHz, D2O, 25 8C): d=À7.60 (s);
MS (MALDI-TOF): m/z=1243.11 [2P+Na]+, 1221.12 [2P+
H]+, 633.07 [P+Na]+, 610.95 [P+H]+; elemental analysis
calcd (%) for C21H18Na3O9PS3·3H2O (664.5): C 37.96, H
3.64; found: C 37.90, H 3.55.
3
7), 130.32 (d, JP, C =5.3 Hz, C-10), 131.37 (s, C-4), 131.5 (d,
2JP, C =28 Hz, C-13), 134.41 (d, 1JP, C =9 Hz, C-1), 134.56 (d,
2
1JP, C =11.3 Hz, C-8), 137.37 (d, JP, C =12.8 Hz, C-9), 140.93 (s,
3
C-2), 143.58 (d, 3JP, C =9.8 Hz, C-12), 146.63 (d, JP, C
=
24.1 Hz, C-6); 31P {1H} NMR (121.5 MHz, D2O, 25 8C): d=
À18.67 (s); MS (MALDI-TOF): m/z=1215.07 [2P+Na]+,
1193.09 [2P+H]+, 618.93 [P+Na]+, 596.91 [P+H]+; elemen-
tal analysis calcd (%) for C20H16Na3O9PS3·3H2O (650.5): C
36.93, H 3.41; found: C 36.85, H 3.33.
Trisodium Salt of Bis(6-methyl-3-sulfonatophenyl)(3-
sulfonatophenyl)phosphane [bis
(Scheme 3)
ACHTRE(UNG o-Me)TPPTS]
To a suspension of magnesium (8.38 g, 0.34 mol, 1.2 equiv.)
in 60 mL of anhydrous THF was introduced under nitrogen
1-bromo-2-methylbenzene (16.5 g, 0.0964 mol, 0.33 equiv.).
Disodium Salt of Bis(6-methyl-3-sulfonatophenyl)(2-
methylphenyl)phosphane [trisACHTRE(UGN o-Me)TPPDS]
After
a
few minutes, the reaction began and 33.5 g
The procedure used to synthesize this product is similar to
that described previously. The reaction mixture was kept at
room temperature only for 3 h under a nitrogen atmosphere.
1H NMR (300 MHz, D2O, 25 8C): d=2.30 (s, 9H H-10, H-3),
6.71 (dd, 3JP, H =5.4 Hz, 3JH-13,H-14 =7.5 Hz 1H, H-14), 7.02
(dd, 3JP, H =4.5 Hz, 4JH-5,H-7 =1.8 Hz, 2H, H-7), 7.11 (t,
3JH-13,H-14 =3JH-12,H-13 =7.5 Hz, 1H, H-13), 7.33 (m, 2H, H-11,
(0.196 mol, 0.66 equiv.) of the 1-bromo-2-methylbenzene in
THF (300 mL) were added dropwise. The reaction mixture
was then heated under reflux for 1 hour. After cooling, phe-
nylphosphorus dichloride (26 g, 0.146 mol, 0.5 equiv.) in
THF (38 mL) was added dropwise and then heated under
reflux for 1 hour. Once the reaction was complete, the mix-
Scheme 3. Synthesis of [bisACHTRE(UNG o-Me)TPPTS].
616
asc.wiley-vch.de
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2008, 350, 609 – 618

Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins
UPDATES
minist›re de l’Øducation nationale, de l’enseignement supØr-
ieur et de la recherche and the UniversitØ d’Artois.
References
[1] a) W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem.
1993, 105, 1588–1609; Angew. Chem. Int. Ed. Engl.
1993, 32, 1524–1544; b) B. Cornils, E. Wiebus, Chem-
tech 1995, 33–38; c) B. Cornils, E. Wiebus, Recl. Trav.
Chim. Pays-Bas 1996, 115, 211–215; d) B. Cornils, J.
Mol. Catal. A: Chem. 1999, 143, 1–10; e) S. Liu, J.
Xiao, J. Mol. Catal. A: Chem. 2007, 270, 1–43.
[2] a) E. G. Kuntz, Chemtech 1987, 17, 570–575; b) V. Mi-
chelet, M. Savignac, J. P. GenÞt, Electronic Encyclope-
dia ofReagents ofr Organic Synthesis , (Eds. L. Pa-
quette, P. Fuchs, D. Crich, P. Wipf), Wiley, New York,
2004.
H-12), 7.39 (dd, 4JP, H =4.5 Hz, 3JH-4,H-5 =7.8 Hz, 2H, H-4),
7.65 (dd, 3JH-4,H-5 =7.8 Hz, 3JH-5,H-7 =1.8 Hz, 2H, H-5); 13C-
3
{1H} NMR (75.5 MHz, D2O, 25 8C): d=20.5 (d, JP, C =3 Hz,
3
C-3), 20.76 (d, JP, C =2.3 Hz, C-10), 126.65 (s, C-5), 127.23 (s,
3
C-13), 129.93 (s, C-7), 130.47 (s, C-12), 130.91 (d, JP, C
=
=
3
2
5.2 Hz, C-11), 131.27 (d, JP, C =4.5 Hz, C-4), 131.80 (d, JP, C
2
4.5 Hz, C-9), 133.76 (s, C-14), 134.15 (d, JP,C =8.3 Hz, C-2),
141.02 (s, C-1), 143.47 (d, 1JP, C =26.4 Hz, C-8), 146.82 (d,
3JP, C =24.9 Hz, C-6); 31P {1H} NMR (121.5 MHz, D2O, 25 8C):
d=À27.38 (s); MS (MALDI-TOF): m/z=1038.74 [2P+
Na]+, 1016.76 [2P+H]+, 530.70 [P+Na]+, 508.72 [P+H]+;
elemental analysis calcd (%) for C21H19Na2O6PS2·2H2O
(544.5): C 46.32, H 4.26; found: C 46.23, H 4.21.
[3] H. Bahrmann, S. Bogdanovic, in: Aqueous-Phase Or-
ganometallic Catalysis, (Eds.: B. Cornils, W. A. Herr-
mann), VCH, Weinheim, 1998, pp 306–321.
[4] a) J. R. Anderson, E. M. Campi, W. R. Jackson, Catal.
Lett. 1991, 9, 55–58; b) E. Monflier, G. Fremy, Y. Cas-
tanet, A. Mortreux, Angew. Chem. 1995, 107, 2450–
2452; Angew. Chem. Int. Ed. Engl. 1995, 34, 2269–
2771; c) M. T. Reetz, S. R. Waldvogel, Angew. Chem.
1997, 109, 870–873; Angew. Chem. Int. Ed. Engl. 1997,
36, 865–867; d) P. Kalck, L. Moquel, M. Dessoudeix,
Catal. Today 1998, 42, 431–440; e) T. Mathivet, C.
MØliet, Y. Castanet, A. Mortreux, L. Caron, S. Tilloy,
E. Monflier, J. Mol. Catal. A: Chem. 2001, 176, 105–
116; f) M. Dessoudeix, M. Urrutigoïty, P. Kalck, Eur. J.
Inorg. Chem. 2001, 1797–1800.
Catalytic Experiments
The water-soluble phosphane (400 mmol, 9 equiv. vs. Pd) was
dissolved in water (2g) in a Schlenk tube under a nitrogen
atmosphere. This solution was then transferred into another
Schlenk tube containing PdACHTER(UNG OAc)2 (44 mmol, 10mg). After
stirring with a magnetic bar for 15h, the obtained yellow so-
lution was transferred into a mixture of allyl undecyl car-
bonate (1.12mmol, 287mg), diethylamine (2,24mmol,
165mg), dodecane (95mg – GC internal standard), heptane
(2g – solvent) and the required amount of Rame-b-CD. The
medium was stirred at 1000 rpm at room temperature and
the reaction was monitored by quantitative gas chromato-
graphic analysis of the organic layer. The initial reaction
rate (mmol·hÀ1) was defined as the amount of allyl undecyl
carbonate converted per hour at 20–30% conversion. The
Rame-b-CD/phosphane ratio has been calculated by consid-
ering the amount of phosphane available in the reaction
medium to interact with the cyclodextrin. Indeed, it was
considered that only 5 equivalents of the phosphane can in-
teract with the cyclodextrin. In fact, three equivalents were
[5] E. Monflier, S. Tilloy, G. Fremy, Y. Castanet, A. Mor-
treux, Tetrahedron Lett. 1995, 36, 9481–9484.
[6] a) E. Monflier, S. Tilloy, C. MØliet, A. Mortreux, S.
Fourmentin, D. Landy, G. Surpateanu, New. J. Chem.
1999, 23, 469–472; b) E. Monflier, S. Tilloy, L. Caron,
J. M. Wieruszeski, G. Lippens, S. Fourmentin, D.
Landy, G. Surpateanu, J. Inclusion Phenom. Macrocy-
clic Chem. 2000, 38, 361–379; c) A. Da Costa, E. Mon-
flier, D. Landy, S. Fourmentin, G. Surpateanu, Surf. Sci.
2001, 470, 275–283.
used to stabilize the palladium(0) species [Pd
one equivalent of the phosphane was oxidized during reduc-
tion of the Pd(OAc)2, according to Eq. (1).
ACHTRE(UGN TPPTS)3] and
[7] E. Monflier, H. Bricout, F. Hapiot, S. Tilloy, A.
Aghmiz, A. M. Masdeu-Bultó, Adv. Synth. Catal. 2004,
346, 425–431.
ACHTREUNG
[8] C. Binkowski, J. Cabou, H. Bricout, F. Hapiot, Eric
Monflier, J. Mol. Catal. A: Chem. 2004, 215, 23–32.
[9] L. Leclercq, M. Sauthier, Y. Castanet, A. Mortreux, H.
Bricout, E. Monflier, Adv. Synth. Catal. 2005, 347, 55–
59.
[10] P. Blach, D. Landy, S. Fourmentin, G. Surpateanu, H.
Bricout, A. Ponchel, F. Hapiot, E. Monflier, Adv.
Synth. Catal. 2005, 347, 1301–1307.
Acknowledgements
[11] D. Kirschner, T. Green, F. Hapiot, S. Tilloy, L. Le-
clercq, H. Bricout, E. Monflier, Adv. Synth. Catal.
2006, 348, 379–386.
[12] L. Leclercq, F. Hapiot, S. Tilloy, K. Ramkisoensing,
J. N. H. Reek, P. W. N. M. van Leeuwen, E. Monflier,
Organometallics 2005, 24, 2070–2075.
M. Ferreira is grateful to the Minist›re de l’Education et de la
Recherche for financial support (2005–2008). The authors are
grateful to G. Crowyn for NMR analysis and to CAPA
(Centre d’Analyse ProtØomique de l’Artois) for mass spec-
trometry analysis. The mass spectrometry facilities used for
this study are funded by the European community (FEDER),
the Fonds d’Industrialisation du Bassin Minier (FIBM), the
[13] K. A. Connors, in: Comprehensive Supramolecular
Chemistry, Vol. 3, (Eds.: J. L. Atwood, J. E. D. Davies,
Adv. Synth. Catal. 2008, 350, 609 – 618
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
617

Michel Ferreira et al.
UPDATES
D. D. MacNicol, F. Vçgtle), Pergamon, Oxford, 1996,
pp 205–241.
[14] H. Gulyµs, A. Szçllçsy, B. E. Hanson, J. Bakos, Tetrahe-
dron Lett. 2002, 43, 2543–2546.
[15] W. A. Herrmann, G. P. Albanese, R. B. Manetsberger,
P. Lappe, H. Bahrmann, Angew. Chem. 1995, 107, 893–
895; Angew. Chem. Int. Ed. Engl. 1995, 34, 811–813.
[20] H. Kinoshita, H. Shinokubo, K. Oshima, Angew. Chem.
2005, 117, 2449–2452; Angew. Chem. Int. Ed. 2005, 44,
2397–2400.
[21] X. Wang, H. Y. Fu, X. Li, H. Chen, Catal. Commun.
2004, 5, 739–741.
[22] V. M. S. Gil, N. C. Oliveira, J. Chem. Educ. 1990, 67,
473–478.
˝
[16] H. Gulyµs, A. Szçllosy, P. Szabó, P. Halmos, J. Bakos,
[23] a) D. Sinou, in: Aqueous-Phase Organometallic Cataly-
sis, (Eds.: B. Cornils, W. A. Hermann), VCH, Wein-
heim, 1998, pp 401–407; b) J. P. GenÞt, M. Savignac, J.
Organomet. Chem. 1999, 576, 305–317.
Eur. J. Org. Chem. 2003, 2775–2781.
[17] H. Gulyas, A. C. BØnyei, J. Bakos, Inorg. Chim. Acta
2004, 357, 3094–3098.
[18] L. R. Moore, K. H. Shaughnessy, Org. Lett. 2004, 6,
[24] L. Leclercq, H. Bricout, S. Tilloy, E. Monflier, J. Col-
225–228.
loid Interface Sci. 2007, 307, 481–487.
[19] E. C. Western, K. H. Shaughnessy, J. Org. Chem. 2005,
70, 6378–6388.
[25] R. Gꢂrtner, B. Cornils, H. Springer, P. Lappe, German
Patent DE 5030, 1982
618
asc.wiley-vch.de
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2008, 350, 609 – 618