Heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-β-cyclodextrin: A genuine supramolecular carrier for aqueous organometallic catalysis

Article abstract of DOI:10.1002/adsc.200505417

The behavior of heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-β- cyclodextrin as inverse phase transfer catalyst in biphasic Tsuji-Trost and hydroformylation reactions has been investigated. In terms of activity, this methylated sulfopropyl ether β-cyclodextrin is much more efficient than the randomly methylated β-cyclodextrin, which was the most active cyclodextrin known to date. From a selectivity point of view, the intrinsic properties of the catalytic system are fully preserved in the presence of this cyclodextrin as the chemo- or regioselectivity was found to be identical to that observed without a mass transfer promoter in the hydroformylation reaction. The efficiency of this cyclodextrin was attributed to its high surface activity and to the absence of interactions with the catalytically active species and the water-soluble phosphane used to dissolve the organometallic catalyst in the aqueous phase.

Full text of DOI:10.1002/adsc.200505417

UPDATES
DOI: 10.1002/adsc.200505417
Heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-b-cyclodextrin:
A Genuine Supramolecular Carrier for Aqueous Organometallic
Catalysis
D. Kirschner,a T. Green,a F. Hapiot,b S. Tilloy,b L. Leclercq,b H. Bricout,b
E. Monflierb,*
a
Department of Chemistry and biochemistry, Institute of Artic Biology, University of Alaska, Fairbanks, AK 99775-5940,
USA
b
´
Universite dꢀArtois, Laboratoire de Physico-Chimie des Interfaces et Applications, FRE CNRS 2485,
´
Rue Jean Souvraz SP 18, 62307 Lens Cedex, France
Fax: þ33-3-2179-1755, e-mail: monflier@univ-artois.fr
Received: October 24, 2005; Accepted: December 15, 2005
Abstract: The behavior of heptakis(2,3-di-O-methyl-
6-O-sulfopropyl)-b-cyclodextrin as inverse phase
transfer catalyst in biphasic Tsuji–Trost and hydro-
formylation reactions has been investigated. In terms
of activity, this methylated sulfopropyl ether b-cyclo-
dextrin is much more efficient than the randomly
methylated b-cyclodextrin, which was the most ac-
tive cyclodextrin known to date. Froma selectivity
point of view, the intrinsic properties of the catalytic
systemare fully preserved in the presence of this cy-
clodextrin as the chemo- or regioselectivity was
found to be identical to that observed without a
mass transfer promoter in the hydroformylation re-
action. The efficiency of this cyclodextrin was attrib-
uted to its high surface activity and to the absence of
interactions with the catalytically active species and
the water-soluble phosphane used to dissolve the or-
ganometallic catalyst in the aqueous phase.
compounds in water, addition of mass transfer promot-
ers is required to obtain commercially viable reaction
rates.[2]
Numerous studies have clearly demonstrated the effi-
ciency of cyclodextrins (CDs) as a mass transfer promot-
er in aqueous phase organometallic catalysis.[3] Indeed,
by forming water-soluble inclusion complexes with
highly hydrophobic substrates, b-CD derivatives greatly
increase the solubility of these compounds in water, and
consequently, avoid mass transfer limitations. Among
the different CDs used in such work, the randomly me-
thylated-b-CD (RAME-b-CD – Figure 1) appeared to
be the most efficient.[4]
The RAME-b-CD was a native b-CD partially O-me-
thylated with statistically 1.8 OH groups modified per
glucopyranose unit. The OH groups in the C-6 position
were fully methylated whereas those in C-2 and C-3 po-
sitions were partially methylated. The outstanding ef-
fect of RAME-b-CD on reaction rates was attributed
to its slight surface activity and to the presence of a
deep hydrophobic host cavity that accommodates prop-
erly the substrate. Nevertheless, RAME-b-CD did not
constitute an optimal solution. Indeed, RAME-b-CD
can forminclusion complexes with the hydrosoluble
phosphane ligands used to dissolve the transition metal
in the aqueous phase.[5] These inclusion complexes were
responsible for the decrease in the linear to branched al-
Keywords: aqueous organometallic catalysis; cyclo-
dextrins; hydroformylation; molecular recognition;
phase-transfer catalysis; Tsuji–Trost reaction
Introduction
During the past decade, ecological requirements have dehydes ratio during the rhodium-catalyzed hydrofor-
pressed chemists to develop clean processes and tech- mylation reaction[6] and a drop in cyclodextrin activity
nologies. In this context, organometallic catalysis in an in some experimental conditions.[7] Consequently, there
aqueous-organic two-phase systemappeared as an envi-
ronmental friendly technique for producing organic with the ligands or the organometallic catalyst.
compounds.[1] Indeed, the organometallic catalyst which
In this context, one of us has reported recently the syn-
is solubilized by hydrophilic ligands in the aqueous thesis of a new methylated derivative of sulfopropyl-b-
is a real interest to find cyclodextrins that do not interact
phase can be easily separated fromthe reaction products
cyclodextrin: heptakis(2,3-di-O-methyl-6-O-sulfoprop-
by simple phase decantation at the end of the reaction. yl)-b-CD (KSPDM-b-CD – Figure 1).[8] This CD con-
However, faced with the insolubility of most organic tains 7 sulfopropyl groups on the primary face and 14
Adv. Synth. Catal. 2006, 348, 379 – 386
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379

D. Kirschner et al.
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Figure 1. Structures of b-cyclodextrin derivatives used in this work.
methyl groups on the secondary face and was able to
form an inclusion complex with organic compounds
such as 2-naphthoic acid. As KSPDM-b-CD possesses
an extended hydrophobic cavity and a structure similar
to that of a surfactant due to the presence of well-iden-
tified hydrophobic and hydrophilic parts, it was of great
interest to compare the behavior of this CD with that of
RAME-b-CD in aqueous-phase organometallic cataly-
sis.
In this paper, the surface activity of KSPDM-b-CD
and its ability to bind to common water-soluble phos-
phanes have been investigated by surface-tension meas-
urements and by NMR spectroscopy, respectively. The
efficiency of KSPDM-b-CD as a mass transfer promoter
in Tsuji–Trost and hydroformylation reactions is also re-
ported.
Figure 2. Surface tensions of aqueous solutions containing
CDs at 258C.
Results and Discussion
centration increased. In fact, the nature of the RAME-
First of all, to evaluate the mass transfer potential of b-CD, having both hydrophobic and hydrophilic moiet-
KSPDM-b-CD, its surface activity has been compared ies, is responsible for its tendency to concentrate at the
to that of other CDs. In Figure 2 are depicted the surface air-water interface. Interestingly, a break of the slope
activities of b-CD, RAME-b-CD and KSPDM-b-CD as was clearly observed at 10À3 MÀ1concentration with
a function of their concentration.
this methylated CD. This break may be associated to
As already reported in the literature,[9] the native b- the formation of aggregates in the bulk solution as ob-
CD exhibited no surface active property as no variation served for classical surfactants or hydrotropic agents.
of the surface tension was observed with this CD what- However, contrary to what is observed with surfactant,
ever the concentration. On the contrary, the curve ob- it must be pointed out that the surface tension did not re-
tained for the RAME-b-CD is characteristic of an ad- main constant above the 10À3 MÀ1 concentration and
sorption phenomenon at the air-water interface as the continued to decrease suggesting that adsorption of
surface tension decreased when the RAME-b-CD con- RAME-b-CD at the interface occurs always above this
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Heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-b-cyclodextrin
UPDATES
concentration. When increasing the concentration of
KSPDM-b-CD in water, a regular decrease in the super-
ficial tension was measured with no aggregation phe-
nomenon in the concentration range 10À4 –10À2 MÀ1
.
More importantly, at high concentrations (>10À3 MÀ1),
its surface activity is higher than that of RAME-b-CD.
The KSPDM-b-CD shape and the high flexibility of
the sulfopropyl arms make KSPDM-b-CD unable to
self-organize in water to generate detectable aggregate
structures in the concentration range 10À4 –10À2 MÀ1
.
As a matter of fact, Shinkai et al. previously showed
with sulfopropylcalixarenes that the existence of a criti-
cal micelle concentration, i.e., a concentration at which
the monomeric molecules aggregate to form micelles
in the bulk solution, required a cone-shape structure
whereas cylindrical molecules did not form such aggre-
gates for concentrations up to 10À2 MÀ1 [10]
.
Second, as it has been demonstrated that inclusions
between RAME-b-CD and phosphanes greatly affected
the performance of catalytic systems,[6,7] an NMR study
has been performed to provide information about the
ability of KSPDM-b-CD to interact with hydrosoluble
phosphane ligands. Two phosphanes widely used in
aqueous organometallic catalysis have been chosen for
this study: the sodiumsalt of the meta-substituted trisul-
fonated triphenylphosphine (TPPTS) and the sodium
salt of the meta-substituted monosulfonated triphenyl-
phosphine (TPPMS). The 31P{1H} NMR spectrumof
TPPTS in the presence of KSPDM-b-CD is displayed
in Figure 3.
Figure 3. Effect of CDs on the 31P{1H} NMR spectrumof
TPPTS (3 mM) in D2O with H3PO4 as external reference:
(a) without CD; (b) with RAME-b-CD (3 mM); (c) with
KSPDM-b-CD (3 mM).
For comparison, the 31P{1H} NMR spectrumof TPPTS
recorded in the presence of RAME-b-CD was also indi-
cated (Figure 3b). The spectrumobtained with RAME-
b-CD showed induced chemical shifts of the 31P NMR
signal of the phosphane which denoted the formation
of an inclusion complex in solution.[11] By contrast, the
31P{1H} NMR spectrumof TPPTS in the presence of
KSPDM-b-CD (Figure 3c) was superimposable to that
without CD (Figure 3a). Similarly, the 1H NMR spectra
of the same mixtures also revealed strong chemical shifts
of the aromatic protons of TPPTS in the presence of
RAME-b-CD (Figure 4b) and no change in the pres-
ence of KSPDM-b-CD (Figure 4c).
To confirmthe 1D NMR results, 2D NMR experi-
ments have been performed to detect spatial interac-
tions between the sulfonated ligands and the modified
b-CDs. In particular, T-ROESY experiments were very
helpful for that purpose.[12] Although the T-ROESY
spectrumof a 1:1 mixture of RAME- b-CD and TPPTS
revealed intense cross-peaks,[11] the observation ofthe T-
ROESY spectrumof a 1:1 mixture of KSPDM- b-CD
and TPPTS showed a complete lack of cross-peaks for
the aromatic protons of the phosphane with any proton
of KSPDM-b-CD. Consequently, KSPDM-b-CD
proved unable to interact with TPPTS to forman inclu-
sion complex.
1
Figure 4. Effect of CDs on the H NMR spectrumof TPPTS
(3 mM) in D2O: (a) without CD; (b) with RAME-b-CD
(3 mM); (c) with KSPDM-b-CD (3 mM).
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D. Kirschner et al.
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The behavior of the KSPDM-b-CD towards the at 258C) compared to that calculated for the RAME-b-
TPPMS ligand was found to be notably different. CD/TPPMS inclusion complex (Ka ¼8000 MÀ1 at
Thus, the chemical shifts observed in the 31P{1H} and 258C).[13]
1H NMR spectra of a KSPDM-b-CD/TPPMS mixture
The absence of interaction between TPPTS and
revealed the formation of an adduct between those KSPDM-b-CD or the poor affinity of KSPDM-b-CD
two compounds. The stoichiometry for this adduct was for TPPMS was rationalized by performing supplemen-
determined by a continuous variation technique (Jobꢀs tary experiments with the permethylated b-CD
1
method). The Jobꢀs plot derived from the 31P{1H} (TRIME-b-CD – Figure 1). The 31P{1H} and H NMR
NMR data showed a maximum at r¼0.5 and a symmet- spectra of a TRIME-b-CD/TPPTS mixture showed
rical shape, indicative of a 1:1 stoichiometry. In order to that TPPTS did not interact with TRIME-b-CD, demon-
determine whether this 1:1 adduct is a true inclusion strating that the absence of interaction between TPPTS
complex or adduct resulting from external interaction and KSPDM-b-CD was due to the permethylation of the
phenomena, a T-ROESYexperiment has also been per- CD secondary face and not to the sulfopropyl groups
formed. The T-ROESY spectrum of a KSPDM-b-CD/ grafted on the primary face. Concurrently, it has also
TPPMS mixture (1:1) proved undoubtedly the forma- been found that the affinity of TRIME-b-CD for
tion of true inclusion complexes between KSPDM-b- TPPMS was notably lower (Ka ¼400 MÀ1 at 258C)
CD and TPPMS (Figure 5).
than that of RAME-b-CD for TPPMS (Ka ¼8000 MÀ1
Indeed, cross-peaks between the non-sulfonated aro- at 258C), confirming that the molecular recognition
matic ring of TPPMS (7.40–7.20 ppm) and two different process is greatly affected by the degree of methylation
groups of CD protons (the methyl groups of the CD and of the CD secondary face.
internal protons of the CD cavity) were clearly observed
Although the TRIME-b-CD cannot interact strongly
(Figure 5). These contacts showed that one of the non- with the phosphane ligands, it is worth mentioning that
sulfonated aromatic rings was included in the cavity TRIME-b-CD cannot be exploited as a mass transfer
whereas the other remained at the periphery of the sec- promoter in aqueous organometallic catalysis because
ondary face. Logically according to the TPPMS struc- of its too low solubility in water at high temperature
ture, weak interactions between some protons of the sul- and its high solubility in organic solvent.[9] By contrast,
fonated ring of TPPMS and the methyl groups protons thanks to the presence of seven sulfonate groups,
of the CD were observed. Finally, no contact was ob- KSPDM-b-CD was highly soluble in water
served between the methylene groups of the alkyl (>10À2 mol/L) and insoluble in organic solvents such
arms and the phosphane, confirming the penetration as heptane or toluene. In addition, the KSPDM-b-CD
of TPPMS by the secondary face of the CD. The stability exhibited interesting surface-tension properties.
constant for this 1:1 inclusion complex was determined
As the KSPDM-b-CD fulfils all requirements for an
by computer fitting of the phosphorus chemical shift ti- application in aqueous organometallic catalysis, this
tration curves and was found to be very low (Ka <50 MÀ1
Figure 5. Partial contour plot of the T-ROESY spectrumof a solution containing KSPDM- b-CD (3 mM) and TPPMS (3 mM)
in D2O at 258C with a 300 ms mixing time. The interactions between the different protons and the deduced orientation of
TPPMS in the CD cavity are also shown.
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Heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-b-cyclodextrin
UPDATES
CD has been used as mass transfer promoter in two or- selectivity than the cleavage of allyl undecyl carbonate.
ganometallic reactions. In particular, the aldehydes selectivity and the linear to
First, catalytic experiments have been carried out to branched ratio (l/b ratio) of aldehyde products are indi-
evaluate the benefit that might be obtained with cative of the nature of the catalytic species and of inter-
KSPDM-b-CD in a Tsuji–Trost reaction. The reaction actions between the CD and the phosphane, respective-
consisted in the cleavage of allyl undecyl carbonate ly.[6] Indeed, we have demonstrated that the l/b ratio de-
that was chosen as a model substrate since it has previ- crease observed in the presence of RAME-b-CD (1.8 vs.
ously been demonstrated that its insolubility in water al- 2.8 without CD) was due to trapping of the phosphane
lows us to detect more easily the effect of a mass transfer ligand by CD and it is suspected that the high aldehydes
promoter in the catalytic solution (Figure 6).[14]
selectivity (97% vs. 59% without CD) is due to an inter-
Reactions were carried out using Pd(OAc)2 as catalyst action between the CD and the catalytic rhodiumspe-
precursor and TPPTS as a ligand. Results were com- cies during coordination of the olefin on the metal cen-
pared to those obtained in the same conditions with ter.
RAME-b-CD and a randomsulfobutyl ether b-CD con-
The hydroformylation experiments were conducted
taining about seven sulfobutyl groups (SBE7-b-CD – using 1-decene as a model substrate in an autoclave
Figure 1). It must be noticed that the SBE7-b-CD exhib- heated at 808C and pressurized with 40 atmof CO/H .
2
its no surface activity and is unable to interact strongly Expected reaction products were undecanal, 2-methyl-
with TPPTS due to electronic repulsions between the decanal and internal decenes which result froman unde-
anionic group of the CD and the sulfonate groups of sired alkene isomerization. The hydrosoluble rhodium
the TPPTS (Ka ¼21 MÀ1 for the SBE7-b-CD/TPPTS catalyst was formed in situ by addition of [Rh(acac)-
couple at 258C).[15] As can be seen in Figure 6, the initial (CO)2] and TPPTS in water. For comparison, the results
activity obtained with KSPDM-b-CD in the cleavage of obtained with SBE7-b-CD and RAME-b-CD were also
allyl undecyl carbonate was 2.5 times higher than that indicated.
measured with RAME-b-CD, which was our best mass
Using RAME-b-CD, a 61% conversion was obtained
transfer promoter to date. Moreover, the reaction mix- with alow 1.8 linear/branched aldehydes ratio and a high
ture is strictly biphasic, separates readily and can be re- 97% chemoselectivity in aldehydes (entry 2 in Table 1).
cycled three times without loss of catalytic activity. Al- By contrast, the conversion obtained with KSPDM-b-
though KSPDM-b-CD and SBE7-b-CD have structural CD was higher (82%), a 60% aldehyde selectivity was
similarities, the former was 13 times more efficient obtained and a 2.6 l/b aldehydes ratio was measured.
than the latter in terms of initial activity.
Actually, the aldehyde selectivity and the l/b aldehydes
The catalytic study has been extended to the hydrofor- ratio were close to those obtained in the hydroformyla-
mylation of linear terminal alkenes which constitutes a tion of 1-decene without CD (compare entries 1 and 4 in
more informative reaction in terms of chemo- and regio- Table 1). As expected, decreasing the amount of
KSPDM-b-CD led to lower activities since the transfer
of the substrate fromone phase to the other constitutes
the rate-determining step of this biphasic reaction. The l/
b aldehyde ratios and the chemoselectivities were unaf-
fected by the amount of KSPDM-b-CD and remained
identical to those observed without CD derivative (en-
tries 4, 5 and 6). In all experiments performed with the
KSPDM-b-CD, it should be pointed out that the phase
separation was fast and that no emulsion was observed
at the end of the reaction. As observed in the Tsuji–Trost
reaction, the effect of the SBE7-b-CD on the conversion
was much less important than that of KSPDM-b-CD or
RAME-b-CD (compare entry 3 with entries 2 and 4).
Surprisingly, the l/b aldehydes ratio decrease observed
with the SBE7-b-CD indicates that this CD modified
the equilibria between the different catalytic species de-
spite its very low capacity to bind to TPPTS ligand.
Figure 6. Effect of various CDs on the relative reaction rate.
The relative reaction rate was defined as the ratio between
The results obtained in the Tsuji–Trost and hydrofor-
the initial catalytic activity in the presence of CD and the in-
mylation reactions demonstrate that the KSPDM-b-CD
itial catalytic activity without CD. The initial catalytic activity
is a much more efficient mass transfer promoter than
without CD is 1.4 mmol/h. Experimental conditions:
Pd(OAc)2 (0.044 mmol), TPPTS (0.401 mmol), CD
(0.176 mmol), water (2 g), allyl undecyl carbonate
(1.12 mmol), diethylamine (2.24 mmol), heptane (2 g) and
dodecane (0.56 mmol – internal standard); T: 208C.
RAME-b-CD and SBE7-b-CD. Indeed, the conversions
were always higher than those obtained with RAME-b-
CD and SBE7-b-CD. Furthermore, KSPDM-b-CD act-
ed as a real mass transfer promoter. Contrary to what
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D. Kirschner et al.
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Table 1. Hydroformylation of 1-decene by Rh(acac)(CO)2/TPPTS system.[a]
Entry
Cyclodextrin
CD/Rh
Conversion[b] [%]
Aldehydes selectivity[c] [%]
l/b aldehyde ratio[d]
1
2
3
4
5
6
(–)
0
12
12
12
6
2
61
21
82
61
18
59
97
57
60
55
57
2.8
1.8
2.1
2.6
2.6
2.7
RAME-b-CD
SBE7-b-CD
KSPDM-b-CD
KSPDM-b-CD
KSPDM-b-CD
3
[a]
Experimental conditions: Rh(acac)(CO)2: 1.1 mmol; TPPTS: 5.5 mmol; water: 0.32 mL; 1-decene: 0.55 mmol; n-undecane
(internal standard): 0.05 mmol; P(CO/H2: 1/1)¼40 bar; T¼808C; Reaction time: 2 hours.
Calculated with respect to the starting olefin.
[b]
[c]
[d]
(Mol. of aldehydes)/(mol. of converted olefins)ꢀ100.
Ratio of linear to branched aldehyde product.
was observed with RAME-b-CD and SBE7-b-CD, Experimental Section
KSPDM-b-CD interacted neither with the catalytic rho-
diumcenter nor with TPPTS since no variation of the al-
dehydes selectivity and the l/b aldehydes ratio was ob-
served with this CD relative to the experiments conduct-
ed without CD.
General Methods
1
The H and 31P NMR spectra were recorded at 300.13 and
1
121.49 MHz on Bruker Avance DRX, respectively. H and
31P{1H} chemical shifts are given in ppm relative to external ref-
erences:sodium3-(trimethylsilyl)propionate- d4 (98% atomD)
in D2O for 1H NMR and H3PO4 in H2O for 31P{1H} NMR. The
2D T-ROESY experiments were run using the software sup-
plied by Bruker. 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
fromthe 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. Gas chromatographic analyses
were carried out on a Shimadzu GC-17A gas chromatograph
equipped with a methyl silicone capillary column (25 mꢀ
0.25 mm) and a flame ionization detector (GC:FID). The in-
terfacial tension measurements were performed using a KSV
Instruments digital tensiometer (Sigma 70) with a platinum
plate. The precision of the force transducer of the surface ten-
sion apparatus was 0.1 mN/m. The experiments were per-
formed at 258Cꢁ0.58C controlled by a thermostatted bath
Lauda (RC6 CS). The samples were freshly prepared by dis-
solving the desired amount of cyclodextrin derivative in ultra-
pure water (Fresenius Kabi, France).
The explanation of these results lies in well-designed
structure of KSPDM-b-CD. Indeed, the permethylation
on the secondary face of KSPDM-b-CD avoided TPPTS
trapping in contrast to what was observed with the par-
tially substituted RAME-b-CD. Moreover, the lipophil-
ic character of the 14 methyl groups on the secondary
face is counterbalanced by the hydrophilic sulfopropyl
arms. The resulting structure is therefore more surface
active than the water-soluble RAME-b-CD or SBE7-b-
CD in the 10À4 –10À2 MÀ1 concentration range, allowing
a better mass transfer between the aqueous and organic
phases.
Conclusion
The results of this structure-activity investigation have
provided compelling evidence that the structure of the
mass transfer promoter is a key aspect of aqueous orga-
nometallic catalysis mediated by cyclodextrin deriva-
tives. KSPDM-b-CD appears as a genuine supramolec-
ular carrier since it does not interact with the hydrosol-
uble ligand or catalytic species and its surface active
properties allow an efficient mass transfer without the
formation of emulsion. Work is currently underway to
exploit these outstanding properties in other biphasic
transition-metal catalyzed reactions.
Materials
D2O (99.95% isotopic purity) was obtained fromMerck. The
sodiumsalt of the meta-substituted trisulfonated triphenyl-
phosphine [TPPTSÀP(m-C6H4SO3Na)3] was synthesized as
reported by Gärtner et al.[16] The sodiumsalt of the meta-
substituted monosulfonated triphenylphosphine [TPPMSÀ
(C6H5)2P(m-C6H4SO3Na)] was prepared by a literature meth-
od.[17] Randomly methylated b-CD (RAME-b-CD) and per-
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Heptakis(2,3-di-O-methyl-6-O-sulfopropyl)-b-cyclodextrin
UPDATES
´
methylated b-CD (TRIME-b-CD) were purchased fromAl-
drich. Randomsulfobutyl ether b-CD (SBE7-b-CD) was pre-
pared according to the general procedure of Stella and Rajew-
ski.[18] The synthesis of heptakis(2,3-di-O-methyl-6-O-sulfo-
propyl)-b-cyclodextrin (KSPDM-b-CD) was described in one
of our previous publications.[8]
Claver, A. M. Masdeu-Bulto, D. Sinou, G. Laurenczy, J.
Mol. Catal. A: Chem. 2003, 195, 113.
[3] a) J. T. Lee, H. Alper, Tetrahedron Lett. 1990, 31, 4101;
b) H. A. Zahalka, K. Januszkiewicz, H. Alper, J. Mol.
Catal. 1986, 35, 249; c) A. Harada, Y. Hu, S. Takahashi,
Chem. Lett. 1986, 2083; d) E. A. Karakhanov, T. Y. Fili-
ppova, S. A. Martynova, A. L. Maximov, V. V. Predeina,
I. N. Topchieva, Cat. Today 1998, 44, 189; e) J. T. Lee, H.
Alper, Tetrahedron Lett. 1990, 31, 1941; f) C. Pinel, N.
General Procedure for the Catalytic Experiments:
´ ´
Gendreau-Diaz, A. Breheret, M. Lemaire J. Mol. Catal.
Tsuji–Trost reaction: Pd(OAc)2 (0.044 mmol, 10 mg), TPPTS
(0.401 mmol, 228 mg), cyclodextrin derivatives (0.176 mmol)
and water (2 g) were introduced under nitrogen atmosphere
into a Schlenk tube. After stirring with a magnetic bar for
1 h, the yellow solution was transferred into a mixture of allyl
undecyl carbonate (1.12 mmol), diethylamine (2.24 mmol),
heptane (2 g) and dodecane (0.56 mmol – internal standard).
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.
Hydroformylation reaction: A stainless 150-mL autoclave,
equipped with a carousel containing 8 vessels with Teflon stir-
ring bar, was used. In a typical experiment, each vessel was
charged with Rh(acac)(CO)2 (1.1 mmol), TPPTS (5.5 mmol)
and cyclodextrin derivatives dissolved in 0.32 mL of water
and the organic phase composed of 1-decene (550 mmol) and
undecane (50 mmol – GC internal standard). The autoclave
was heated at 808C and pressurized with 40 atmof CO/H 2 (1/
1). The time corresponding to the addition of CO/H2 was con-
sidered as the beginning of the reaction. The mixture was stir-
red for 2 h at 808C. The reaction medium was sampled after the
reaction for GC analyses of the organic phase after decanta-
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