Water-soluble phosphane-substituted cyclodextrin as an effective bifunctional additive in hydroformylation of higher olefins

Article abstract of DOI:10.1039/c7cy01108c

In cyclodextrin (CD)-mediated aqueous biphasic catalysis, favoring contacts between the CD ("host"), the organic substrate ("guest") and the water-soluble catalyst is crucial for the reaction to proceed efficiently at the aqueous/organic interface. Grafting the catalyst onto the CD backbone thus appears as an attractive approach to favor the molecular recognition of the substrate and its subsequent catalytic conversion into products. In this context, a new water-soluble β-CD-based phosphane was synthesized and characterized by NMR, tensiometric and ITC measurements. The β-CD-based phosphane consisted of a 3,3′-disulfonatodiphenyl phosphane connected to the primary face of β-CD by a dimethyleneamino spacer. Intra- and intermolecular inclusion processes of one of the two sulfophenyl groups into the β-CD cavity were identified in water. However, the association constant (K_a) related to the β-CD/sulfophenyl group couple was low. Accordingly, the inclusion process was easily displaced upon coordination to rhodium complexes. The efficacy of the resulting Rh-complex coordinated by β-CD-based phosphanes was assessed in Rh-catalyzed hydroformylation of higher olefins. The catalytic system proved to be far more successful and efficient than a system consisting of supramolecularly interacting phosphanes and CDs. The catalytic activity was up to 30-fold higher while the chemo- and regioselectivities remain rather unchanged.

Full text of DOI:10.1039/c7cy01108c

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Potier, S. Menuel, H. BRICOUT, C. B. MACHUT, D. Landy, S. Tilloy, E. Monflier and F. Hapiot, Catal. Sci.
Technol., 2017, DOI: 10.1039/C7CY01108C.
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Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
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Water-soluble Phosphane-Substituted Cyclodextrin as Effective
Bifunctional Additive in Hydroformylation of Higher Olefins
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a
a
a
c
a
J. Leblond, J. Potier, S. Menuel, H. Bricout, C. Machut-Binkowski, D. Landy, S. Tilloy, E.
a
a
Monflier and F. Hapiot *
DOI: 10.1039/x0xx00000x
In cyclodextrins (CDs)-mediated aqueous biphasic catalysis, favoring contacts between the CD ("host"), the organic
substrate ("guest") and the water-soluble catalyst is crucial for the reaction to proceed efficiently at the aqueous/organic
interface. Grafting the catalyst onto the CD backbone thus appears as an attractive approach to favor the molecular
recognition of the substrate and its subsequent catalytic conversion into products. In this context, a new water-soluble β-
CD-based phosphane was synthesized and characterized by NMR, tensiometric and ITC measurements. The β-CD-based
phosphane consisted of a 3,3'-disulfonatodiphenyl phosphane connected to the primary face of the β-CD by a
dimethyleneamino spacer. Intra- and intermolecular inclusion processes of one of the two sulfophenyl groups into the β-
www.rsc.org/
CD cavity were identified in water. However, the association constant (K ) related to the β-CD/ sulfophenyl group couple
a
was low. Accordingly, the inclusion process was easily displaced upon coordination to rhodium complexes. The efficacy of
the resulting Rh-complex coordinated by β-CD-based phosphanes was assessed in Rh-catalyzed hydroformylation of higher
olefins. The catalytic system proved to be far more successful and efficient than a system consisting of supramolecularly
interacting phosphane and CD. The catalytic activity was up to 30-fold higher while the chemo- and regioselectivities
remain
rather
unchanged.
especially found application in organometallic catalysis. They
8
showed great ability to coordinate to various metals such as
Introduction
9
,10
11
12
13
14
Pt, Rh, Ru or Ag, and form effective catalysts in
Pd,
Despite the huge amount of works dealing with cyclodextrins
CDs), these cyclic oligosaccharides continue to attract much
numerous catalyzed reactions such as Suzuki–Miyaura
(
1
0
12
couplings, hydroformylation or ring opening metathesis
attention because of their molecular recognition properties
and the impressive range of applications they offer. Efforts to
make these molecular hosts even more versatile prompted
chemists to investigate their substitution by organic
fragments, variable in type and number. The synthesis of
substituted CDs is nowadays well mastered. Large amounts of
1
3
polymerization.
For years, our group has been investigating phosphane-
substituted CDs and their utilization as ligands and additives in
1
5,16,17,18
aqueous biphasic catalysis.
that CDs substituted on their primary face act both as first-
coordination-sphere ligands through coordination of
We have especially shown
a
randomly methylated
β-CD (DIMEB), heptakis(2,3,6-trimethyl)-β-CD (TRIMEB),
hydroxypropyl- -CD (HP-CD), peracetylated -CD (per-O-Ac-
CD), and sulfobutylether- -CD (SBE- -CD) are industrially
β-CD (RAMEB), heptakis(2,6-dimethyl)-
phosphanyl group onto the metal and as second-coordination-
sphere ligands because of the inclusion of a guest molecule
β
β
β-
1
substrate or ligand) inside their cavity. This approach, first
9
(
β
β
2
0,21
initiated by Reetz et al.,
is now part of a broader concept
produced each year. While random substitution of CDs is quite
easy to implement, the selective modification of CD is a more
difficult task because of their highly-functionalized and
2
2
termed as “supramolecular catalysis”. The goal is to create a
highly specific local environment around the metal to favor the
conversion of the substrate upon inclusion, and possibly the
selectivity. However, the utilization of such phosphane-
functionalized CDs in aqueous media is not as simple to
implement as might appear. As underscored by Reetz,
phosphane-functionalized CDs are very weakly soluble in
1
symmetrical nature. However, methodologies are now at
hand to selectively substitute CDs’ glucopyranose units by a
2 3 4 5 6 7
wide range of moieties. , , , , , Phosphane-substituted CDs
1
7
water. Polar organic solvents such as DMF are then required
with detrimental effects on the reusability of the catalytic
system. Moreover, the molecular recognition is critically
dependent upon the nature of the phosphane substituent.
Scheme 1 illustrates inclusion processes that may control the
extent of hindrance that the CD-host experiences as it
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1
1
upon temperature increase from 25 to 65 °C (Figures 2a-c). Figure 3. P{ H} spectrum of 2 (10 mM) at 25 °C a) after 15 min in
However, the phenomenon was not reversible as, after 1 h at O, b) after 20 min in DMF-d7, and c) after 1 h in DMF-d7.
5 °C, returning to room temperature gave the signal
D
2
6
Accordingly, the resonance at -19.3 ppm was attributed to a
attributed to 2b (Figure 2d). This suggested that the resonance
at -21.4 ppm corresponded to an unstable kinetic species 2a
while that at -22.3 and -22.8 ppm corresponded to more stable
conformation (2d) for which the phosphane-substituent was
not included into a CD cavity ("free" form). Deductively, 2a, 2b
and 2c logically corresponded to conformations displaying
their phosphane-substituent included into a CD cavity.
thermodynamic species 2b and 2c
.
Addition of sodium adamantane carboxylate (AC, 5 equiv/
2) in
D O substantiated the above observations. AC is well known to
2
4
-
strongly interact with the β-CD cavity in water (K = 3.8 10 M
a
1
29
.
)
Once AC was included into the CD cavity, the phosphane-
substituent could no longer interact with the CD cavity and
3
1
1
remained outside. Indeed, the P{ H} signal attributed to 2d
was detected at -18.8 ppm, a value very close to that found in
DMF-d7 (-19.3 ppm). The 2D T-ROESY spectrum confirmed the
absence of cross-peaks between the phosphane-substituent
and the inner protons of the CD cavity (H-3 and H-5) while
intense cross-peaks were apparent between AC and H-3 and
H-5 (Figure 4).
3
Figure 2. P{ H} spectrum of
1
1
2
2
(10 mM) in D O a) at 25 °C after
15 min, b) at 45 °C after 20 min, c) at 65 °C after 20 min, and d)
after slowly cooling down the aqueous solution to 25 °C.
Additional NMR measurements were carried out to get more
information about 2a, 2b and 2c. Upon dissolution of 2 in
DMF-d7, an intense resonance could be detected at -19.3 ppm
along with two other less intense resonances at -20.3 and -
Figure 4. 2D T-ROESY spectrum of a mixture of 2 and sodium
20.8 ppm (Figure 3b). Over time, the resonance at -19.3 ppm
adamantyl carboxylate (AC) (1/5 ratio, total concentration = 10
became predominant (Figure 3c). DMF is well-known to be a
1
dissociating" solvent, meaning that the inclusion process
6
mM) at 25 °C in D
The structures of 2a
determined by isothermal titration calorimetry (ITC). A freshly
prepared sample of (8.1 mM) was first heated in water at 20
C to exclusively form 2b (-22.3 ppm) and 2c (-22.8 ppm). The
2
O.
"
,
2b and 2c were unambiguously
was greatly disfavoured, as confirmed by the absence of
correlations on the T-ROESY spectrum (ESI, Figure S9).
2
°
aqueous solution was then brought back to room
temperature. Successive dissolutions in water resulted in a
series of spikes of heat flow indicative of a dissociation process
(ESI). The pattern of the heat effects as a function of the
concentration fitted a mathematical model involving two
supramolecularly interacting molecules (inter-inclusion).
Accordingly, 2b and 2c were described as supramolecular
3
0
dimers displaying a sulfophenyl group included into the CD
cavity of another molecule (Scheme 3). Given the background
studies on inclusion processes between sulfonated
3
1,32
phosphanes and
β
-CDs,
we tentatively attributed 2b to the
dimer for which the sulfophenyl groups was included through
the secondary face (more probable situation). The less
abundant 2c could be a dimer with the sulfophenyl groups
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1
Figure 5. P spectrum of a mixture of 2 (10 mM) and Rh(CO)
2
(acac)
products resulting from isomerization of the carbon-carbon
double bond). Note that no hydrogenated product was
detected. Interestingly, the regioselectivity remained high with
(
2
2 mM) at 25 °C after 15 min in D O.
1
Given the value of the JP-Rh coupling constant, the structure of l/b ratios from 2.3 to 2.6. It can be inferred that the low
the Rh-complexes was probably Rh(PN)(CO)(acac) and affinity of the phosphane moiety for the
β
-CD cavity (see
(CO) (acac) . The doublet at 44.9 ppm was attributed above) prevented the displacement of equilibriums towards
to a rhodium center coordinated by only one . A double low phosphane-coordinated Rh-species responsible for the
coordination of on the Rh center was hypothesized for the formation of branched aldehydes.
doublet at 44.6 ppm as its intensity increased with the amount observed using -CD and non-grafted phosphanes such as
of . Note that the absence of correlation in the ROESY TPPTS (l/b = 1.7). Using 10 eq of
+
- 31
Rh(PN)
2
2
5
3
2
The opposite was
β
3
5
2
2 with respect to Rh, the
spectrum clearly shows that the equilibriums taking place conversion was low (10%, entry 5) because the equilibriums
between the CD cavity and the grafted-phosphane were easily were displaced towards less active high phosphane-
displaced by the coordination of the phosphane on the Rh coordinated rhodium species. Beneficial effects were logically
center.
noticed on both the chemoselectivity (93%) and the
regioselectivity (2.9) because of the more hindered
coordination sphere around the rhodium center. As expected,
hydroformylation of 1-decene was faster at higher reaction
temperature (110 °C, entries 6 and 7). However, the
Hydroformylation of higher olefins
With more than 11 million tons aldehydes produced each year,
the catalytic hydroformylation of olefins has become one of
the popular industrial reactions taking place under
subsequent decrease in the 2/1-decene association constant
3
9
(van’t Hoff equation) logically gave higher concentrations of
substrate outside the cavity, resulting in higher proportions of
alkene isomers and branched aldehydes (l/b = 2.1, entry 7). To
reveal the molecular recognition existing between the CD
cavity and the substrate, a catalytic experiment was carried
homogeneous
conditions.
Of
interest
is
the
Ruhrchemie/Rhône-Poulenc aqueous biphasic process
developed in the 80's that converts propene to n-
butyraldehyde and isobutyraldehyde in the presence of a
rhodium-catalyst retained in the aqueous phase by the
benchmark phosphane TPPTS (the sodium salt of the
out in the presence of one equiv AC with respect to
2 (entry 8).
4
0
The significant decrease in conversion was indicative of the
competition between AC and the substrate. Noticeably, this
also indirectly proved the inclusion of the substrate into the CD
trisulfonated triphenylphosphane). Although this process is
suitable for the conversion of lower olefins (<C5), it proved to
be ineffective to convert higher olefins because of obvious
insolubility issues. In this context, methods have been
cavity during the course of the reaction. While the low CO/H
2
4
1
pressure did not influence the conversion, chemo- and
regioselectivities were slightly modified under 20 bar CO/H2.
As expected, the l/b ratio slightly increased to 3.0. Indeed, at
low CO partial pressure, the equilibriums were shifted to the
developed to overcome the problem. Last developments in
4
2,43
the field include micro-emulsions,
4
rhodium single-atom
4
45
hydrogels,
ionic liquids,
catalyst,
amphiphilic core-shell polymer
48
nanofiltration,
4
6
47
latexes,
thermomorphic
51
4
9 50
high-phosphane coordinated species HRh(CO)(2)2 which was
solvent systems, , and mechanochemistry. Our group has
for long been involved in the development of aqueous biphasic
systems for hydroformylation of higher olefins, especially using
responsible for the preferential formation of linear aldehydes.
a
5
2
Table 1. Rh-catalyzed hydroformylation of 1-decene.
CD. To compare the properties of the studied catalytic
system to those of previously described CD/TPPTS
combinations, we performed Rh-catalyzed hydroformylation of
1
-decene (model substrate) under aqueous biphasic
conditions. First, a “blank” catalytic test was carried out using
-CD and in the presence of Rh(CO) (acac) at 80 °C under 50
bar of CO/H (1:1) pressure. No conversion was observed
indicative of the poor ability of the -CD/ combination to
form effective Rh-catalysts at the aqueous/organic interface
Table 1, entry 1). Second, the catalytic performance of was
assessed under similar catalytic conditions. As expected,
β
1
2
Entry Component
Time
h)
Conv.
(%)
0
Ald. sel. l/b
(%)
2
(
β
1
1
2
3
4
β-CD +
1
3
-
-
(
2
2
2
2
3
47
81
82
84
2.3
2.6
2.4
2
6
68
allowed to overcome the mass transfer issue between the
aqueous compartment and the organic phase (entries 2-4).
24
99
b
5
6
7
2
2
2
6
3
6
10
79
93
60
53
2.9
2.8
2.1
c
Contacts between the HRh(CO)
x
(
2)
y
catalytic species and the
c
substrate included into the CD host were greatly favored at the
aqueous/organic interface with beneficial effects in
hydroformylation of terminal double bonds. By itself, this
result validated our strategy consisting in grafting the catalytic
species to the CD backbone. The chemoselectivity was also
high as aldehydes were mainly formed (along with side-
100
d
8
9
1
2
2
2
+ AC
3
3
3
26
23
49
80
91
82
2.6
3.0
2.6
e
f
0
g
1
1
1
2
2
2
3
3
45
45
84
78
2.2
2.5
h
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i
1
3
2
3
42
75
(0.0115 mmol, 3 mg), β-CD and 1 (5
2.5
limited by the mass transfer between the organic and the
aqueous phase. The only contribution capable of overcoming
a
Conditions: Rh(acac)(CO)
eq/Rh each) or
2
2
(5 eq/Rh), water (6 mL), 1-decene (815 mg, mass transfer issues was the molecular recognition existing
b
5
00 eq/Rh), P(CO/H ) = 50 bar, 80 °C, 1500 rpm. 10 eq of between the CD cavity and the substrate alkyl chain. No
c
/Rh. 110 °C. AC (adamantane carboxylate, 1 eq/2). contribution involving putative supramolecular amphiphiles
2
d
2
e
f
) = 20 bar. Rh(COD)
g
P(CO/H
h
2
2
BF
4
as a rhodium precursor. 80 could be invoked. Indeed, surface-tension measurements of
and alkenes of different chain
lengths did not show any decrease in the surface tension, even
at high concentration of (ESI, Figure S11). Note that, as
bar. performed using the aqueous phase recovered from aqueous solution containing
2
i
entry 2. performed using the aqueous phase recovered from
2
entry 12.
observed for 1-decene, hydroformylation of 1-octadecene
carried out at 100 °C led to higher conversion but lower
selectivities (Table 2, entry 6).
Considering Rh(COD)
Rh(CO) (acac) did not substantially modified the catalytic
performance (entry 10). Similar conclusions could be drawn
when increasing the CO/H pressure from 50 to 80 bar (entry
1). Experiments were also carried out to evaluate the
2 4
BF as a rhodium precursor instead of
2
Accordingly, compared with previous procedures described in
the literature, the main advantages of the present catalytic
system lie in i) the use of water to solubilize the
organometallic catalyst, ii) the easy separation of the product-
containing organic phase and the catalyst-containing aqueous
phase, and iii) its reusability.
2
1
reusability of the catalytic system. For this purpose, the
biphasic system stemming from hydroformylation of 1-decene
(
Table 1, Entry 2) was decanted and the organic phase was
withdrawn. The aqueous phase was reinjected into the
autoclave with fresh substrate and the reaction was restarted Conclusions
Table 1, entry 12). After 3 h reaction time, the same
(
Throughout this study, we managed to greatly improve the
catalytic performance in Rh-catalyzed hydroformylation of
higher olefins by employing a functionalized supramolecular
receptor capable of both coordinating to organometallic
species and recognizing organic substrates via supramolecular
procedure was repeated (Table 1, entry 13). Analysis of the
two recovered organic phases clearly established the
robustness of the catalytic system. Only a slight erosion of the
conversion and chemoselectivity was noticed because of the
partial oxidation of
2
inherent to the recycling process.
means. The receptor consists of a
primary face by a sulfonated phosphane, making them ideal
Table 2. Rh-catalyzed hydroformylation of hydrophobic olefins for use as both first- and second-sphere ligands. Our system
β-CD substituted on its
a
using
2
as a phosphane.
allows overcoming the main pitfalls highlighted by Reetz
almost twenty years ago for CD-grafted phosphanes. The
hydrophilicity of CD-grafted sulfonated phosphane greatly
improve the water solubility and prevents the inclusion of the
phosphane into the CD cavity under catalytic conditions, a
Entry Substrate
Conv.
%)
Ald.
sel. (%)
81
61
57
58
58
54
l/b
(
1
2
3
4
5
1-decene
47
55
47
32
29
96
2.3
2.5
2.6
2.6
2.5
1.6
1-dodecene
1-tetradecene
1-hexadecene
1-octadecene
1-octadecene
phenomenon typically observed with
β-CD and non-grafted
phosphane such as TPPTS. Accordingly, the equilibrium
between the active Rh-species is not perturb by the
CD/phosphane association and the regioselectivity remains
high. The results of this structure-activity investigation have
provided compelling evidence that the competition between
the substrate and the ligand with respect to the molecular
receptor can be circumvent by using a carefully chosen CD-
substituent. Further investigations to extend the scope of
these catalytic systems are currently in progress.
b
6
a
Conditions: Rh(acac)(CO)
2
(0.0115 mmol, 3 mg), 2 (5 eq/Rh),
water (6 mL), substrate (500 eq/Rh), P(CO/H ) = 50 bar, 80 °C,
2
b
500 rpm, 3 h. 100 °C.
1
The catalytic system was then extended to hydroformylation
of more hydrophobic olefins. The results are summarized in
Table 2. It is very instructive to observe that the conversion of
1-dodecene was higher than that observed for 1-decene (55%
vs 47%, respectively, see Table 1). These results were very
different from what was previously observed using randomly
Experimental
3
5
methylated
that case, 1-decene had been converted more efficiently than In a Schlenk tube, anhydrous mono-iodide β-CD (900 mg, 0.7
-dodecene, suggesting that the molecular recognition process mmol), (313 mg, 0.7 mmol) and sodium carbonate (307 mg,
of the two substrates was different comparing and RAME-
2.9 mmol) were dissolved in 30 mL anhydrous DMF under
β-CD (RAME-β
-CD) in combination with TPPTS. In Synthesis of the phosphane-grafted CD (2)
1
1
2
β-
CDs. On the other hand, in line with our previous results, nitrogen. The solution was heated at 80 ° C for 18 h. After
further increasing the length of the alkyl chain logically led to cooling down the system to room temperature, dropwise
lower conversions (from 55% for 1-dodecene to 29% for 1- addition of 50 mL anhydrous acetone afforded a white
octodecene) because of the higher hydrophobicity. Such precipitate. After decantation, the supernatant was removed.
behavior was characteristic of a biphasic catalytic system The content of the tube was then filtered on a frit under
6
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nitrogen and the resulting solid was washed with 5×20 mL of
degassed acetone to remove traces of DMF. To remove
inorganic salts, the solid was dissolved in 20 mL of water.
Selective precipitation of
2 was carried out by subsequent
addition of 100 mL of an acetone/water (9:1) mixture. The
resulting solid was dried under vacuum in a Schlenk tube to
give 2 as a white powder (75% yield, 836 mg).
Catalytic experiment
In a typical experiment, Rh(CO)
2
(acac) (3 mg, 0.012 mmol) was
cycles and dissolved in a
(90 mg, 0.058 mmol) in water (6 mL).
degassed three times by vacuum-N
degassed solution of
2
2
4
5
The resulting solution was stirred at room temperature until all
the rhodium complex was dissolved (2 h). The substrate (8.5
M. Řezanka, Eur. J. Org. Chem., 2016, 5322–5334.
J. Potier, S. Menuel, N. Azaroual, E. Monflier and F. Hapiot,
mmol) was poured into the autoclave and N
catalytic solution was then cannulated under nitrogen into the
autoclave. Once the desired temperature was reached, the Gaudino and G. Cravotto, ACS Sustainable Chem. Eng., 2016,
autoclave was pressurized under CO/H
(1:1) pressure 4, 919–929.
typically 50 bar) and the solution was vigorously stirred (2500
rpm). When the reaction was complete, the apparatus was Chem. Eur. J., 2014, 20, 2565–2573.
-purged. The Eur. J. Org. Chem., 2014, 1547-1556.
2
6
L. Jicsinszky, M. Caporaso, K. Tuza, K. Martina, E. Calcio
2
7
(
M. Jouffroy, D. Armspach, A. Louati, D. Matt and L. Toupet,
8
cooled down to room temperature and depressurized. The
1
M. Jouffroy, D. Armspach and D. Matt, Dalton Trans., 2015,
products were analyzed by H and C NMR experiments. All 44, 12942–12969.
13
9
runs were performed at least twice in order to ensure
reproducibility.
M. Jouffroy, D. Armspach, D. Matt, K. Osakada and D.
Takeuchi, Angew. Chem. Int. Ed., 2016, 55, 8367–8370.
1
0
E. Zaborova, J. Deschamp, S. Guieu, Y. Blériot, G. Poli, M.
Ménand, D. Madec, G. Prestat and M. Sollogoub, Chem.
Commun., 2011, 47, 9206–9208.
C. L. Yang, Y. K. Cheung, J. Z. Yao, Y. T. Wong and G. C. Jia,
Acknowledgements
1
1
The University of Artois is acknowledged for supporting and
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Région Nord – Pas de Calais and FEDER are acknowledged for
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Table of contents entry
Cyclodextrins substituted by a sulfophenyl phosphane show excellent recognition ability
towards higher olefins in aqueous biphasic Rh-catalyzed hydroformylation.