Ditopic cyclodextrin-based receptors: New perspectives in aqueous organometallic catalysis

Article abstract of DOI:10.1002/adsc.201000027

The mass transfer properties of mono- and ditopic β-cyclodextrin-based receptors have been evaluated in a biphasic palladium-catalyzed Tsuji-Trost reaction and compared to one of the best mass-transfer promoters, namely the randomly methylated β-cyclodextrin. While monotopic receptors appeared to be poor mass-transfer promoters of long alkyl chain allyl carbonates or urethanes, cooperative effects have been evidenced with ditopic cyclodextrin-based receptors, opening new perspectives in aqueous organometallic catalysis.

Full text of DOI:10.1002/adsc.201000027

FULL PAPERS
DOI: 10.1002/adsc.201000027
Ditopic Cyclodextrin-Based Receptors: New Perspectives in
Aqueous Organometallic Catalysis
a,b,c
a,b,c
a,b,c
a,b,c
Natacha Six,
Stꢀphane Menuel,
Hervꢀ Bricout,
Frꢀdꢀric Hapiot,
a,b,c,
and Eric Monflier
Universitꢀ de Lille Nord de France, 59000 Lille, France
CNRS UMR 8181, Unitꢀ de Catalyse et de Chimie du Solide – UCCS, Facultꢀ des Sciences Jean Perrin, rue Jean
Souvraz, SP 18, 62307 Lens Cedex, France
UArtois, UCCS, Facultꢀ des Sciences Jean Perrin, rue Jean Souvraz, SP 18, 62307 Lens Cedex, France
Fax : (+33)-3-2179-1755; phone: (+33)-3-2179-1772; e-mail: eric.monflier@univ-artois.fr
*
a
b
c
Received: January 13, 2010; Revised: May 3, 2010; Published online: June 8, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201000027.
Abstract: The mass transfer properties of mono- and effects have been evidenced with ditopic cyclodex-
ditopic b-cyclodextrin-based receptors have been trin-based receptors, opening new perspectives in
evaluated in a biphasic palladium-catalyzed Tsuji– aqueous organometallic catalysis.
Trost reaction and compared to one of the best
mass-transfer promoters, namely the randomly me-
thylated b-cyclodextrin. While monotopic receptors Keywords: cooperative effects; cyclodextrins; host-
appeared to be poor mass-transfer promoters of long guest systems; inclusion compounds; structure-activi-
alkyl chain allyl carbonates or urethanes, cooperative ty relationships; supramolecular chemistry
Introduction
To circumvent this technological lock, more elabo-
rated CD structures have been recently synthesized
The design of environment-benign and ecological starting from the mono-azide b-CD and terminal al-
chemical processes has become a major challenge in kynes using the Cu(I)-catalyzed azide-alkyne cycload-
[
8]
our present consuming world. In this context, the use dition. Herein, we evaluate the catalytic performan-
of water as non-polluting solvent was thought to be ces of the synthesized mono- and ditopic b-CD-based
the most obvious solution for transition metal-cata- receptors in a Pd-catalyzed cleavage reaction of alkyl
[1]
lyzed reactions. Nevertheless, the insolubility of allyl carbonates (Scheme 1). The two main parame-
most organic molecules in water limits its industrial ters controlling the efficiency of the supramolecular
use to the transformation of hydrophilic substrates. b-CD receptors are discussed, namely their ability to
Although solutions have been developed for hydro- adsorb at the organic/aqueous interface and the ease
[
2]
phobic substrates, none of the proposed solutions with which a substrate is included in their cavities. We
was completely satisfying. For example, the use of bring proof of the synergetic interactions displayed by
molecular receptors such as chemically modified b-cy- well-designed ditopic CD-based receptors to supra-
clodextrins (b-CDs) has been intensely investigated molecularly recognize long alkyl chain substrates and
[
3]
during the past decade. In fact, CDs can mask the efficiently convert them into products.
substrate hydrophobic character by including the hy-
drophobic moiety in their cavity, thus favoring interfa-
cial catalysis. Interesting results were obtained in vari-
ous catalytic reactions such as aldehyde hydrogena-
[
4]
[5]
tion, olefin hydroformylation or allyl carbonate
[
6]
cleavage (Tsuji–Trost reaction). However, with very
hydrophobic substrates, the catalytic performances
are significantly affected.
[
7]
Scheme 1. The Tsuji–Trost reaction.
Adv. Synth. Catal. 2010, 352, 1467 – 1475
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Results and Discussion
The structure of the CDs used in this study are de-
scribed in Scheme 2 (see also Supporting Informa-
tion). Only randomly methylated derivatives have
been considered as it has previously been clearly es-
tablished that their adsorption properties at the or-
ganic/aqueous interface are better than those of their
[
9]
hydroxylated counterparts. Apart from the well-
known randomly methylated b-CD (RAME-b-CD),
all the CDs are mono-substituted on their primary
face by a triazole group, itself substituted in the 4-po-
sition by various organic moieties.
The Tsuji–Trost reactions have been performed at
room temperature under nitrogen using palladium
acetate as catalyst, TPPTS (sodium salt of the meta-
trisulfonated triphenylphosphine) as hydrosoluble
ligand, diethylamine as allyl scavenger and undecyl
(
8), tridecyl (9), hexadecyl (10) and octadecyl (11)
Figure 1. Conversion of allyl undecyl carbonate (8) as a
allyl carbonates as substrates. In Figure 1 are summar-
ized the catalytic results obtained with monotopic b-
CDs receptors 1–4 and RAME-b-CD, one of the best additives.
function of time in a Pd-catalyzed cleavage reaction with
RAME-b-CD (-·-·-), 1 (-^-), 2 (-*-), 3 (- -) and 4 (- -) as
~
&
mass-transfer promoters. Using 8 as a substrate,
RAME-b-CD appears a better mass-transfer promot-
er than 1–4. Among the triazole randomly methylated
b-CDs, 2, 3 and 4 give similar results while 1 appears
less efficient. Note that without CD, the conversion is
only 0.5% after 3.5 h. Tensiometric measurements
have been carried out to tentatively explain the above
results.
As shown in Figure 2, all the curves describing the
variation of the surface tension (g) as a function of
the concentration are gathered in a quite narrow
beam, suggesting that the surface active properties of
these mono-substituted b-CDs is not the determining
factor influencing the mass transfer between the or-
Scheme 2. Mono- and ditopic b-CDs. DS: degree of substitu-
tion.
Figure 2. Surface tension curves of RAME-b-CD (-·-·-), 1
A
H
U
G
R
N
N
&
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Ditopic Cyclodextrin-Based Receptors: New Perspectives in Aqueous Organometallic Catalysis
ganic and the aqueous phase. In fact, the lower effi-
ciency of 1–4 with respect to RAME-b-CD is a conse-
quence of the steric hindrance generated by the sub-
stituted triazole group. The approach of the substrate
is then disfavored for the recognition process to take
place. Moreover, a capping process of the CD cavity
by the triazole substituant has also been highlighted.
This phenomenon has especially been evidenced for 2
through a detailed NMR analysis. Varying the concen-
tration of 2 in D O results in a cross shift of two
2
broad signals in the triazole proton chemical shift
1
range in the H NMR spectrum, indicative of two dif-
ferent species A and B in slow equilibrium (Figure 3).
From a 2D T-ROESY NMR experiment, it can be in-
ferred that A is a self-included structure as correla-
tion peaks were identified between the triazole
moiety and the CD cavity, contrary to B (non-includ-
ed form) for which no correlation could be detected
À1
Figure 4. Partial T-ROESY spectrum of 2 (36 mmol·L ) in
D O at 258C.
2
(
Figure 4). The magnitude in chemical shift variation
for each signal confirms this assertion as Dd is larger
for B (0.3 ppm) than for A (0.05 ppm), which is logi-
cally attributed to a greater dependence of the more
water-exposed B form towards the concentration. At
À1
a low 5 mmol·L concentration, the proportions of A
and B were determined by integration of the triazole
1
signals in the H NMR spectrum. A slight excess of A
(
54% vs. 46% for B) was calculated. Note that no var-
iation in the NMR signal was detected when increas-
ing the temperature (even at 808C) suggesting a
rather strong interaction of the triazole moiety with
À1
the CD cavity. Of interest, at 5 mmol·L , both signals
evolve, after 20 days, to a predominant resonance that
has been attributed to another species C. The struc-
ture of C could be deduced from a comparison of its
triazole proton resonance with that obtained from a
1
Figure 5. Partial H NMR spectra at 258C in D O of 5 mM
2
1
:1 mixture of 2 and RAME-b-CD (Figure 5). Actual-
solutions of freshly prepared 2 (top), 2 after 20 days
ly, with 2 and RAME-b-CD in stoichiometric propor- (middle) and freshly prepared equimolar mixture of 2 and
tions, the free RAME-b-CD cavity is available and RAME-b-CD (bottom).
the triazole substituent of 2 has then a natural tenden-
cy to include inside this cavity rather than the cavity
of its own CD. The self-inclusion process (A form) is
then disfavored. As both the triazole proton resonan-
ces of C and the above mixture could be nearly super-
imposed, we contend that the triazole substituent of
C is embedded in the cavity of another 2 receptor
[
10]
(
inter-inclusion) (Scheme 3).
A 2D T-ROESY spectrum of C unambiguously
confirms the inclusion of the triazole group as cross
peaks were detected between the triazole proton and
the inner protons of the CD (H-3 and H-5) (see Sup-
porting Information). As a conclusion, 2 is a mixture
of self-included and non-included structures whose
Figure 3. Chemical shift variation of 2 in water at 258C as a proportions depend upon the concentration and the
function of the concentration.
time in solution.
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Natacha Six et al.
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Scheme 3. Equilibriums between the non-included form A
and self-included forms B and C.
This capping phenomenon has also been highlight-
ed with 1 (see Supporting Information). In that case,
integration of the triazole protons led to 72% of self-
included form and 28% of CDs with their substituent
Figure 6. Impact of 3 on the cleavage reactions of 8 (-*-), 9
(-
&
-), 10 (-~-) and 11 (-^-).
free in solution. Conversely, the effect is less marked seemed appropriate to use ditopic species such as 5, 6
for the more hydrophilic receptors 3 and 4 as no con- and 7. The closeness of two CDs linked together by a
tacts were detected in their T-ROESY spectra. This is short organic tether should improve the substrate rec-
1
corroborated by the H NMR spectrum as only one ognition process. Moreover, the linker being attached
triazole signal was detected suggesting 100% of the to another CD moiety, its self-inclusion process (cap-
free form. Nevertheless, although not included, the ping) should be disfavored.
presence of the sulfonated or carbohydrate triazole
Very interestingly, the catalytic performances of
group over the primary face of the CD significantly these ditopic b-CD-based receptors are in high con-
hampers the substrate recognition. Consequently, 3 trast with those obtained with their monotopic coun-
and 4 are better mass-transfer promoters than 1 and 2 terparts (Figure 7). Note that, for the results to be
but remain less efficient than RAME-b-CD. Hence, comparable, the molar amount of RAME-b-CD was
the lower catalytic efficiency of 1–4 with respect to twice that of the dipotic receptors. A host structure-
RAME-b-CD is a consequence of both steric effects dependent recognition process seems to occur during
and a partial capping phenomenon of the CD cavity the cleavage reaction. As evidenced through the anal-
by the triazole substituent. The substrate recognition ysis of the initial activities, RAME-b-CD is more ap-
process is then hindered, resulting in lower initial ac- propriate than the ditopic receptors to recognize 8
tivities.
and 9, indicative of a better ability to mask the hydro-
The use of monotopic receptors has been extended phobic character of middle-length alkyl chain sub-
[
12]
to the Pd-catalyzed cleavage reaction of 9, 10 and 11. strates. Conversely, RAME-b-CD and 6 give similar
With 3 as mass-transfer promoter, increasing the alkyl results for the Pd-catalyzed cleavage of 10 while 5
chain length has a detrimental impact on the initial and 6 prove more efficient than RAME-b-CD to help
activity, indicative of a bad substrate recognition pro- converting 11 into alcohols, suggesting cooperative ef-
cess at the interface (Figure 6). Similar results have fects resulting from synergetic interactions between 5
been obtained with 4 as additive (see Supporting In- or 6 and the substrates. Hence, RAME-b-CD appears
formation). Thus, in addition to the above capping inappropriate to recognize subtrates with long alkyl
phenomenon, this outcome illustrates the requisite chains since the catalytic activity decreases when the
adequacy between the CD host and the guest sub- substrate alkyl chain is lengthened. On the contrary,
strate. Long alkyl chain substrates are too large to be with the ditopic b-CDs as receptors, almost no varia-
properly accommodate in a single CD cavity. In fact, tion in catalytic performances is noticed whatever the
two CD-based receptors would be needed as demon- length of the substrate alkyl chain. For example, when
strated in the solid state with 1,12-dodecanediol as the conversion remains rather constant with 6 after
[
11]
guest.
In solution, the inclusion process of a long 3.5 h reaction time (in the range 47–64%), the conver-
sion measured with RAME-b-CD dramatically drops
alkyl chain into two CDs is statistically disfavored.
Hence, monotopic CD-based receptors suffer from from 100 to 29% when increasing the alkyl chain
several drawbacks and do not constitute a viable al- length from eleven to eighteen carbons. Also note
ternative to promote the mass transfer at the aque- that the p-isomer receptor 7 leads to poor activities
ous/organic interface. To circumvent this difficulty, it whatever the substrates.
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Ditopic Cyclodextrin-Based Receptors: New Perspectives in Aqueous Organometallic Catalysis
Figure 8. Surface tension curves of 5 (-
-), 6 (-*-) and 7
&
AHCTUNGTRENNUNG
(-~-) in water at 208C.
Figure 8 definitely confirms that, here again, the
surface active properties of the mass-transfer promot-
ers do not constitute the key parameter allowing a
satisfactory explanation of the catalytic results.
Indeed, no significant difference could be detected as
the three curves are superimposed over a broad con-
centration range. However, contrary to what was
demonstrated with monotopic receptors, no clear evi-
dence of a self-inclusion process was established for 5,
1
13
6
and 7 as H and C NMR prove inappropriate to
bring clues on their geometry as the spectra show
most of the resonances to be clustered together,
giving very broad and shouldered peaks. Nonetheless,
a comparison with their hydroxylated counterparts for
which contacts were previously detected on the T-
ROESY spectrum tend to prove that at least a partial
inclusion of the linker in the CD cavities may occur,
[
8a]
especially for the p-isomer 7.
other previous studies on bridged bis
which the substituent is also embedded in the CD
This is in line with
AHCTUNGTR(EUNNNG b-CD)s for
[
13]
cavity.
Thus, when comparing the catalytic results obtained
with 5, 6 and 7, it appears that the structure of the di-
topic host is of importance as it governs the substrate
recognition process and consequently the catalytic
performances of the system. In particular, it can be
assumed from the catalytic results that the recognition
process of long alkyl chain substrates occurs accord-
ing to a “sandwich” binding mode for 5 and 6
[
14]
(
Scheme 4a). Actually, in that case, the linear sub-
strate can probably penetrate deeply into the b-CD
cavities from the longitudinal direction to be fully in-
Figure 7. Structure/activity dependence of RAME-b-CD
A
H
N
T
E
N
N
&
-), 6 (-*-) and 7 (-~-) on the cleavage reactions
Adv. Synth. Catal. 2010, 352, 1467 – 1475
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Natacha Six et al.
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Scheme 6. Possible cyclic supramolecular intermediate be-
tween ditopic receptors 5, 6 and 7 and the branched sub-
strate 13.
Scheme 4. “Sandwich” binding mode (a) and host-linker-
guest co-inclusion mode (b).
are 4-fold more efficient than RAME-b-CD at con-
verting branched urethanes into amines. The poor
ability of RAME-b-CD to recognize branched struc-
[
16]
cluded at the end of the recognition process. This tures was previously demonstrated. Conversely, the
channel-type supramolecular assembly displays a high results obtained with 5, 6 and 7 are far better than ex-
binding ability through the cooperative binding of pected and suggest that a bent structure favors the co-
two adjacent CD units, resulting in increased contacts operativity existing between two linked CDs. Thus,
between the substrate and the organometallic catalyst. when a “sandwich” binding mode is believed to take
These results are in line with previous studies where place for 12, we propose an “open wings” cyclic
well-suited bridged bis(CD)s displayed an enhanced supramolecular structure as intermediate of the rec-
molecular binding ability for large substrates through ognition process between the n-hexyl chains of 13 and
the cooperativity of two hydrophobic cavities located the CD cavities of 5, 6 and 7 (Scheme 6 and Figure 9).
[
15]
in a closely vicinity.
Contrary to linear substrates such as 8–11, note
Conversely, a host-linker-guest co-inclusion binding that the bent structure of 13 allows unblocking of the
mode (Scheme 4b) is certainly preferred for 7 as the CD cavities of 7 as an increase in activity was ob-
initial activity is low whatever the alkyl chain length. served. This is in sharp contrast with the above results
In that case, the linker caps one of the CD cavities, obtained with linear substrates and for which no in-
preventing the substrate to be properly recognized.
crease in activity was noticed for 7. The molecular
Extension of the above results to other hydropho- recognition process between 7 and 13 likely involves
bic substrates such as urethanes gave us valuable in- two interactions, the first interaction with the host
sights into the recognition process involving ditopic guiding the second one. Indeed, once an n-hexyl
CDs. Two sets of experiments have been carried out. chain is included in a CD cavity, the other chain
The first one concerned the linear allyl-dodecyl-ure- could then be able to expel the triazole group from
thane 12 and the one the branched allyl-dihexyl-ure- the second CD cavity. Its hydrophobic character
thane 13 (Scheme 5).
being properly masked, 13 could then efficiently react
The results obtained with 12 are in good agreement with the palladium catalyst.
with what was observed above with carbonates. The
ortho-isomer 6 is still the best mass-transfer promoter
while the para-isomer 7 remains the worst. However, Conclusions
in these conditions, RAME-b-CD and 6 have a simi-
lar ability to recognize 12, the performances of To sum up, the use of ditopic b-CD-based receptors
RAME-b-CD slightly decreasing with time.
appears a promising approach to solve the mass-trans-
Of interest, the catalytic results obtained with 13 fer limitation in aqueous organometallic catalysis pro-
clearly demonstrated that ditopic receptors 5, 6 and 7 vided that the receptor conformation was appropriate
with the substrate geometry. Two tethered CDs are
much more efficient as mass-transfer promoters than
RAME-b-CD to recognize substrates that are too
large to be accommodated in a single CD cavity but
are less efficient than RAME-b-CD in binding small
substrates which can be completely included in a
single cavity. This unambiguously proves that multiple
Scheme 5. Linear and branched alkyl-allyl-urethanes.
simultaneous hydrophobic interactions have collective
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Ditopic Cyclodextrin-Based Receptors: New Perspectives in Aqueous Organometallic Catalysis
Figure 9. Impact of RAME-b-CD (-*-), 5 (-
-), 6 (-*-) and 7 (-~-) on the cleavage reactions of 12 and 13.
&
ing. Mass spectra were recorded on a MALDI-TOF/TOF
Bruker Daltonics Ultraflex II in positive reflectron mode
with 2,5-DHB as matrix. Gas chromatographic analyses
properties whose contribution to the mass-transfer
process is greater than that displayed by individual in-
teractions for which the constituents interact monova- were carried out on a Shimadzu GC-17A gas chromato-
lently. This study constitutes the first example of co- graph equipped with a methyl silicone capillary column
operative hydrophobic interactions between two CD (25 mꢂ0.25 mm; film thickness: 0.25 mm) and a flame ioni-
zation detector (GC:FID).
cavities and a substrate at the organic/aqueous inter-
face of a biphasic system. Thus, thanks to cooperative
effects exhibited by ditopic hosts, an important gap
could be filled in biphasic catalysis, especially for the
transformation of very hydrophobic substrates.
A
Synthesis of Sodium [1-(Randomly Methylated 6 -
Deoxy-b-d-cyclodextrinyl)-1H-1,2,3-triazol-4-yl]-
methanesulfonate (3)
A
Randomly methylated mono-6-azido-6 -deoxy-b-d-cyclodex-
trin (1.5 mmol) and hydrated copper sulfate (3 mmol) were
Experimental Section
added to
1.8 mmol) in DMF (40 mL). After the subsequent dropwise
addition of a freshly prepared solution of sodium ascorbate
6 mmol) dissolved in water (5 mL), the solution was stirred
for 18 h at room temperature. After evaporation of the sol-
vent, the crude product was dissolved in an ammonia solu-
tion (8%) and stirred 2 h before being purified by column
chromatography on silica gel with water as eluent to give
the product as a white powder. After evaporation of the sol-
vent, the product was dissolved in 25 mL of water and ex-
tracted by 500 mL of chloroform (2ꢂ250 mL). The organic
a
solution of sodium propargylsulfonate
All chemicals were purchased from Strem Chemicals and
Aldrich Chemicals in their highest purity. Distilled water
was used in all experiments. All solvents and liquid reagents
were degassed by bubbling nitrogen for 15 min before each
use or by two freeze-pump-thaw cycles. The syntheses of 1,
(
(
[8]
2
, 5, 6 and 7 have previously been described. NMR spectra
were recorded on a Bruker DRX300 spectrometer operating
at 300 MHz for H nuclei, 75 MHz for C nuclei and
1
1
13
31
21.49 MHz for P nuclei. CDCl (99.50% isotopic purity),
3
DMSO-d (99.80% isotopic purity) and D O (99.92% iso-
6
2
topic purity) was purchased from Euriso-Top. Signals are re-
corded in terms of chemical shifts and are expressed in parts
per million (d), multiplicity, coupling constants (in Hz,
rounded to one decimal place), integration and assignments
in that order. The correct assignments of the chemical shifts
were confirmed when necessary by two-dimensional correla-
phases were collected, dried with anhydrous Na SO , filtered
2
4
and concentrated. The product was dissolved in 50 mL of
water and 25 g of Amberlyst 15 resin (Na form) was then
added. The resin was filtered off on a glass filter and
washed with 15 mL of water. The solution was lyophilized to
1
1
1
1
13
give a yellowish powder; yield: 1.25 g (55%). H NMR
tion measurements attained by H- H COSY, H- C HSQC
1
13
or H- C HMBC experiments. The 2D T-ROESY experi-
ments were run using the software supplied by Bruker. T-
ROESY experiments were preferred to classical ROESY ex-
periments as this sequence provides reliable dipolar cross-
peaks with a minimal contribution of scalar transfer. Mixing
times for TROESY experiments were set at 300 ms. The
data matrix for the T-ROESY was made of 512 free induc-
tion 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 process-
(300 MHz, D O): d=8.12 (s, 1H), 5.34 (m, 5.1H), 5.02 (m,
2
4.1H), 4.60 (m, 4.6H), 4.06–3.92 (m, 13.2H), 3.83–3.39 (m,
1
3
57.8H), 3.21–3.12 (m, 5.7H), 2.43–2.28 (m, 2.4H); C NMR
(75.5 MHz, CDCl , 208C): d=140.1, 126.8, 103.2–101.3,
84.2–79.3, 74.3, 73.4–70.9, 61.6–59.1, 52.0, 47.9, 29.9;
MS: m/z (%)=1478.51 (2.2) (calcd. for [C56 NaO37S +
NaO37S+
3
H
N
N
N
(calcd.
94
96
98
3
+
Na] : 1478.51), 1492.93 (27.2) (calcd. for [C57
H
3
+
Na] : 1492.52), 1506.96 (60.1) (calcd. for [C58
H
NaO37
S
3
+
+
Na] :
1506.54),
1520.97
(9.5)
for
+
[C H N NaO S+Na] : 1520.56), 1534.98 (0.9) (calcd. for
5
9
100
3
37
+
[C H N NaO S+Na] : 1534.57).
6
0
102
3
37
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Natacha Six et al.
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A
Synthesis of N-[1-(Randomly Methylated 6 -Deoxy-
b-d-cyclodextrinyl)-1H-1,2,3-triazol-4-yl]methyl-d-
gluconoamide (4)
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A
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added to a solution of the N-propargyl-d-gluconoamide
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(
(
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vent, the crude product was dissolved in an ammonia solu-
tion (8%) and stirred 2 h before being purified by column
chromatography on silica gel with water as eluent to give
the product as a white powder. After evaporation of the sol-
vent the product was dissolved in 50 mL of water and ex-
tracted by 500 mL of chloroform (2ꢂ250 mL). The organic
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2
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2
4
and concentrated to give a yellowish powder; yield: 1.85 g
77%). H NMR (300 MHz, D O): d=7.97 (s, 1H), 5.33 (m,
.5H), 4.98 (m, 5.4H), 4.56 (m, 4.0H), 3.18 (m, 3.2H), 3.99–
.86 (m, 17.5H), 3.71–3.53 (m, 69.9H), 3.37–3.14 (m,
9.4H); C NMR (75.5 MHz, CDCl , 208C): d=173.0,
44.0, 124.8, 102.6–100.7, 92.9–81.4, 79.0, 73.8, 72.7, 71.3,
0.3, 63.3, 60.8, 59.7–58.7, 50.0, 31.1. MS: m/z (%)=1570.06
4.1) (calcd. for [C H N O +Na] : 1569.63), 1584.09
25.5) (calcd. for [C H N O +Na] : 1583.64), 1593.11
1
(
2
6
3
2
1
7
13
3
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+
6
3
108
4
40
9
24–945 (open access: http://www.mdpi.com/2071–
+
62.0) (calcd. for [C H N O +Na] : 1597.66), 1612.12
6
4
110
4
40
1
050/1/4/924); c) A. Behr, J. Leschinski, C. Awungacha,
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Palladium-Catalyzed Tsuji–Trost Reaction
The TPPTS water-soluble phosphane (0.32 mmol) was dis-
solved in water (2.56 g) in a Schlenk tube under a nitrogen
atmosphere. This solution was then transferred into another
Schlenk tube containing Pd ACHTUNGTRENN(UNG OAc) (0.036 mmol). After stir-
2
ring with a magnetic bar for 15 h at room temperature, the
obtained solution was transferred into a mixture of alkyl
allyl carbonate (1.80 mmol), diethylamine (3.60 mmol), do-
decane (0.75 mmol – GC internal standard) and heptane
3.2 g). The medium was vigorously stirred (1000 rpm) at
room temperature and the reaction was monitored by quan-
titative gas chromatographic analysis of the organic layer.
2
001, 7, 1797–1800.
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This work was supported by the Centre National de la Re-
cherche Scientifique (CNRS) and the Ministꢀre de l’Enseigne-
ment Supꢁrieur et de la Recherche. The Agence Nationale de
la Recherche is also thanked for financial support (ANR-07-
CP2D-05-02). Roquette Frꢀres (Lestrem, France) is gratefully
acknowledged for generous gifts of cyclodextrins. We thank
Grꢁgory Crowyn for NMR experiments. Finally, we would
like to thank the anonymous reviewer for his or her valuable
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ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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