Telomerisation of 1,3-butadiene with 1,4:3,6-dianhydrohexitols: An atom-economic and selective synthesis of amphiphilic monoethers from agro-based diols

Article abstract of DOI:10.1002/cssc.201100135

The telomerisation of 1,3-butadiene with a Pd/TPPTS catalytic system in water or an organic solvent was used for the synthesis of C8 ethers from isosorbide, an agro-based diol. The use of water/oil biphasic reaction conditions allowed the selective synthe

Full text of DOI:10.1002/cssc.201100135

DOI: 10.1002/cssc.201100135
Telomerisation of 1,3-Butadiene with 1,4:3,6-
Dianhydrohexitols: An Atom-Economic and Selective
Synthesis of Amphiphilic Monoethers from Agro-Based
Diols
Jonathan Lai,[a, b] Sandra Bigot,[a] Mathieu Sauthier,*[a] Valꢀrie Molinier,*[b] Isabelle Suisse,[a]
Yves Castanet,[a] Jean-Marie Aubry,[b] and Andrꢀ Mortreux[a]
Dedicated to Christian Bruneau on the occassion of his 60th birthday.
The telomerisation of 1,3-butadiene with a Pd/TPPTS catalytic
system in water or an organic solvent was used for the synthe-
sis of C8 ethers from isosorbide, an agro-based diol. The use of
water/oil biphasic reaction conditions allowed the selective
synthesis of monoethers with improved rates upon using inor-
ganic bases as promotors. As isosorbide is a non-symmetric
diol, the two hydroxyl groups display different reactivities. 2-O-
substituted-monoethers were preferentially obtained if water
was used as the solvent, whereas in DMSO 5-O-substituted
monoethers were the major products. Complete conversions
of isosorbide with up to 94% monoether selectivities were ob-
tained. The optimized reaction conditions were successfully ap-
plied to isomannide and isoidide for the selective synthesis of
the derived ethers. An improved reactivity of the endo-hydroxy
groups of isosorbide and isomannide versus the exo-hydroxy
groups of isosorbide and isoidide was observed if the reaction
was performed in DMSO instead of water.
Introduction
The palladium catalysed telomerisation reaction is a straight-
forward and atom-economic synthetic tool for the production
of alkyl octadienyl ethers from an alcohol and 1,3-dienes
(Scheme 1).[1] With methanol and 1,3-butadiene, the transfor-
diols derived from starch. Using a diol as a substrate is attrac-
tive, since it lowers the number of possible reaction products,
and it also yields interesting mono-substituted compounds. In
the case of petroleum-based glycols[6,3e] the telomerisation re-
action proved to be an efficient pathway to glycol ethers,
which are highly effective organic solvents due to their affinity
for hydrophilic and lipophilic organic compounds with numer-
ous applications (e.g., paints, inks, nail polish, de-icers, medi-
cine). However, the established or suspected toxicity of some
of them constitutes a serious limitation for their future devel-
opment. Alternative compounds from agro-based diols are of
strong interest and this prompted us to focus our attention on
the valorisation of 1,4:3,6-dianhydro-d-glucitol (isosorbide),
1,4:3,6-dianhydro-d-mannitol (isomannide), and 1,4:3,6-dianhy-
dro-d-iditol (isoidide).
Scheme 1. The telomerisation reaction.
mation was recently industrialised for the production of 1-
octene after a further hydrogenation and methanol elimination
step. The cost effectiveness of the telomerisation reaction
arises from the relatively low cost of 1,3-butadiene compared
to previously used ethylene and the efficiency of the catalysts
in terms of activities, robustness, and selectivities. In addition
to the very efficient and simple palladium/PPh3 catalytic
system, other phosphine- and carbene-modified catalysts have
recently allowed further improvements.[2] As an alternative to
methanol, hydrophilic polyols readily available from agro-re-
sources have, in the context of sustainable chemistry, attracted
particular attention. Polyols with three or more hydroxyl
groups,[3] sucrose,[4] as well as starch[5] are suitable substrates
under homogeneous or biphasic conditions. However, to date,
reactions have not been reported on 1,4:3,6-dianhydrohexitols
(isosorbide, isomannide, and isoidide), which are agro-based
Isosorbide is a V-shaped water-soluble asymmetric diol that
bears two intracyclic ether functions. Industrially obtained
from the double dehydration of sorbitol, isosorbide is an agro-
based diol, which can potentially be used in place of glycols. It
[a] J. Lai, S. Bigot, Dr. M. Sauthier, Dr. I. Suisse, Prof. Y. Castanet,
Prof. A. Mortreux
Unitꢀ de Catalyse et Chimie du Solide, UMR CNRS 8181
Universitꢀ Lille Nord de France, ENSCL
BP 90108, 59652 Villeneuve d’Ascq (France)
Fax: (+33)3-20-33-63-01
E-mail: mathieu.sauthier@univ-lille1.fr
[b] J. Lai, Dr. V. Molinier, Prof. J.-M. Aubry
Chimie Molꢀculaire et Formulation, EA 4478
Universitꢀ Lille Nord de France, ENSCL
BP 90108, 59652 Villeneuve d’Ascq (France)
1104
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Synthesis of Amphiphilic Monoethers
has already found important applications, after chemical modi-
fications, as a vasodilator (isosorbide dinitrate),[7] monomer,
and more specifically as polycondensates (polyesters),[8] plasti-
cisers, or solvents (diesters and diethers of isosorbide, and in
particular dimethylisosorbide),[9] and shows potential for fur-
ther new applications. We previously reported the synthesis of
isosorbide monoethers by direct alkylation of isosorbide with
bromoalkanes and showed the “solvo-surfactant” properties of
these compounds.[10] These procedures allowed the synthesis
of products with high purity, but suffered from a rather limited
efficiency and chemoselectivity; the monoethers were ob-
tained with low yields and as a mixture with the diether. In ad-
dition, the synthesis was not environmentally friendly, as large
amounts of wastes, mainly salts, were produced. To access iso-
sorbide OÀC8 monoethers or diethers with high atom econo-
my, selectivities, and chemical yields, we thus turned our atten-
tion to the telomerisation reaction of isosorbide with 1,3-buta-
diene. Difficulties arise with isosorbide in comparison to other
diols from the fact that this substrate bears two secondary hy-
droxyl groups that are supposed to be less reactive than pri-
mary alcohols. In addition, the molecule is not symmetric and
the two hydroxyl groups are consequently not equivalent, thus
increasing the number of products that can be obtained
(Scheme 3). The reaction is also performed on isomannide and
isoidide, two C2-symmetric isomers of isosorbide (Scheme 2).
sor in the liquid phase was ensured by the addition of 0.5 mL
of a 1m aqueous solution of sodium hydroxide. The reaction
was performed by using 25 mmol isosorbide in the presence
of 0.2% [Pd(OAc)2] associated with four equivalents of TPPTS
at 808C, and the reactor was fed by a continuous flow of 1,3-
butadiene at atmospheric pressure. This procedure was advan-
tageous for practical reasons as commonly used glassware
equipments were involved, thus avoiding the use of any high-
pressure equipment.[11]
The reaction yielded linear diether 4aa and the two mono-
ethers 2a and 3a as the main products (Scheme 3). These
compounds were isolated from the crude product by using
distillation under reduced pressure and purified by using silica
gel chromatography.
The corresponding branched isomers of 2, 3, and 4 were
formed in low amounts (<3%) and were hard to separate and
obtain as pure compounds. Octadienol and products of the
butadiene dimerisation were obtained as volatiles in rather lim-
ited amounts and were easily separated from the ethers
during the distillation procedure. Under these conditions, as
the mixture remained homogeneous, the formation of the
products could be monitored by using GC analysis of aliquot
samples taken at different reaction times (Figure 1). As expect-
ed, the initial products were the monoethers 2 and 3. Howev-
er, the reactivities of the exo-2-hydroxy group of isosorbide
and the sterically shielded and hydrogen-bonded endo-5-hy-
droxy group were different. In the case of the telomerisation
reaction in the presence of water, the exo-2-hydroxy group
tends to be the more reactive, and monoethers 2 was ob-
tained as the major isomer. After 4 h, the amount of monoeth-
ers reached a maximum as their formation was counterbal-
anced by their conversion to diethers 4. The yield of diethers 4
finally reached 60% and did not increase further even at
higher reaction times, probably because of catalyst deactiva-
tion as indicated by the forma-
Scheme 2. Structures of 1,4:3,6-dianhydro-d-glucitol (isosorbide), 1,4:3,6-dia-
nhydro-d-mannitol (isomannide), and 1,4:3,6-dianhydro-d-iditol (isoidide).
tion of a black precipitate after
6 h.
Faster reaction rates are ex-
pected if
a
stoichiometric
amount of 1,3-butadiene is intro-
duced at the beginning of the
reaction. Experiments were thus
carried out in a 100 mL stainless
steel autoclave under the same
reaction conditions of tempera-
ture, catalyst loading, and reac-
tants, with the initial loading of
5 equivalents of 1,3-butadiene.
At the early stage of the reac-
Scheme 3. Reaction products obtained from the telomerisation of 1,3-butadiene with isosorbide.
Results and Discussion
tion, part of the 1,3-butadiene remains liquid (even at 808C ac-
cording to the volume of the reactor). In addition, isosorbide is
a hydrophilic compound with very limited solubility in alkanes,
and the miscibility of liquid isosorbide with 1,3-butadiene at
808C, although not known, is expected to be rather limited,
particularly in the presence of water. The reaction mixture was
thus biphasic at the beginning of the reaction. Due to the
presence of the two phases, samples taken in the autoclave
The telomerisation reaction was initially performed in melted
isosorbide without any additional organic solvent. As the com-
monly used triphenylphosphine ligand showed very limited
solubility in isosorbide, we thus turned to a more hydrophilic
phosphine, the TPPTS [tris(3-sulfonatophenyl)phosphine hy-
drate, sodium salt], initially used in our group for sucrose telo-
merisation.[4] The solubility of the ligand and palladium precur-
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M. Sauthier, V. Molinier et al.
total conversion of isosorbide was observed, and a 51% yield
of diether 4 was obtained. Further increases of the concentra-
tion of sodium hydroxide did not allow the formation of a no-
tably larger amount of diether compared to monoether. This
demonstrates that with 0.165 mmol sodium hydroxide, the re-
action had reached its maximum yield within 2 h. It should be
noted that, even with this amount of sodium hydroxide, the
base was added in catalytic amounts, which corresponded to
only 3.3 equivalents of hydroxide anions per palladium. Other
metal hydroxides can be used, but do not increase the yields
of diether 4 nor do they improve the selectivities for the mon-
oethers 2 or 3 (Table 1, entries 6–9).
~
*
Figure 1. Evolution of isosorbide 1 ( ), 2-monoether 2 ( ), 5-monoether 3
&
*
(
), and diether 4 ( ) during the telomerisation reaction under atmospheric
The reaction was performed at three different temperatures,
and to avoid the total consumption of the starting material,
the runs were quenched and analysed after 30 min reaction
time (Table 2). The experiment at 808C evidenced that reasona-
1,3-butadiene pressure (composition of the mixture in %). The dotted lines
are drawn to guide the eye. The reaction was performed at 808C with
25 mmol isosorbide, 0.2 mol% [Pd(OAc)2] (vs isosorbide), 0.8 mol% TPPTS,
and 0.5 mL aqueous 1m NaOH (0.5 mmol).
Table 1. Effect of the base on the selectivity in the telomerisation reac-
tion of 1,3-butadiene with isosorbide catalysed by [Pd(OAc)2]/4 TPPTS.[a]
Table 2. Temperature effect on the telomerisation reaction of 1,3-buta-
diene with isosorbide catalysed by [Pd(OAc)2]/4 TPPTS.[a]
Entry Base
[mmol]
Conversion[b] of 1
[%]
Selectivity[b] [%]
Mono/di
(2+3)/4
Entry
T
Conversion[b]
Selectivity[b] [%]
Mono/di
2
3
4
[8C]
of 1 [%]
2
3
4
(2+3)/4
1
2
3
4
5
6
7
8
9
No base
NaOH (0.025)
NaOH (0.05)
68
72
88
74
78
67
40
43
32
35
54
46
23
18
27
9
10
8
10
27
23
3
4
6
51
47
60
55
19
31
36
22
16
1
1.1
0.7
0.8
4.3
2.2
1
2
3
80
65
50
99
24
5
51
66
75
37
32
25
12
2
<2
7.3
49
n.d.
NaOH (0.165) 100
NaOH (0.3)
NaOH (0.5)
LiOH (0.5)
KOH (0.5)
CsOH (0.5)
100
100
99
93
100
[a] The reactions were performed with 25 mmol isosorbide, 125 mmol
1,3-butadiene, 0.2 mol% palladium (vs isosorbide), 0.8 mol% TPPTS, and
0.5 mL of aqueous NaOH (1m) for 30 min. [b] Conversions and selectivi-
ties were determined by using GC analysis.
[a] The reactions were performed at 808C with 25 mmol isosorbide,
125 mmol 1,3-butadiene, 0.2 mol% palladium (vs isosorbide), 0.8 mol%
TPPTS, and 0.5 mL water with the appropriate base for two hours.
[b] Conversions and selectivities were determined by using GC analysis.
bly high reaction rates could be attained in the telomerisation
reaction of 1,3-butadiene with isosorbide. Although this deriva-
tive is a secondary alcohol, turnover frequencies of 1000 mol
of isosorbide converted per mol of palladium per hour were
obtained under these conditions. As expected, decreasing the
reaction temperature led to drastically reduced conversions of
isosorbide.
are not representative of the whole reaction mixture and
changes in the composition during the reaction could not be
monitored. Conversion of 1 and yields of the corresponding
ethers were thus measured after running the reaction for two
hours (Table 1). For all experiments, because of a large con-
sumption of 1,3-butadiene, the pressure dropped from 10 bar
(1 bar=105 Pa) to less than 3 bar, and the reaction mixture was
homogeneous after being vented.
With the aim to reinforce the formation of a biphasic system
beneficial to achieve higher monoether/diether (mono/di)
ratios, additional experiments were performed by using an or-
ganic solvent (ethyl acetate) or increasing the water content
(Table 3). Under such conditions, a biphasic water/oil system
was maintained during the reaction. As the catalyst is immobi-
In the absence of a base, the conversion of isosorbide
reached 68% after two hours
(Table 1, entry 1). Monoethers 2
Table 3. Selectivity in the telomerisation reaction of 1,3-butadiene with isosorbide using [Pd(OAc)2]/4 TPPTS
and 3 were obtained as main
products and only 3% diether 4
was formed. The introduction of
a strong base had a marked
effect on the reaction rates. The
introduction of sodium hydrox-
ide in the range from 0.025 to
0.165 mmol dissolved in 0.5 mL
of water improved the reaction
rate further. In a 0.165 mmol so-
lution of sodium hydroxide, the
under reinforced biphasic conditions.[a]
Entry
Solvent
t
Conversion[b]
Selectivity[b] [%]
Mono/di
(mL/mL)
[h]
of 1 [%]
2
3
4
(2+3)/4
1
2
3
4
AcOEt/H2O (20/0.5)
AcOEt/H2O (20/0.5)
AcOEt/H2O (20/0.5)
H2O (4)
3
29
90
3
33
46
99
99
57
56
58
65
43
43
38
28
<1
<1
3.2
6.6
–
–
30
14
[a] The reactions were performed with 25 mmol isosorbide, 125 mmol 1,3-butadiene, 0.2 mol% palladium (vs
isosorbide), 0.8 mol% TPPTS and given amounts of aqueous 1m NaOH and AcOEt at 808C. [b] Conversions and
selectivities were determined by using GC analysis.
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Synthesis of Amphiphilic Monoethers
lized in the aqueous phase by means of the water soluble
TPPTS/Pd system, it may be anticipated that, by using this pro-
cedure, the monosubstituted products 2 and 3 formed in the
course of the reaction could be extracted from the water
phase containing the catalyst, thus preventing their subse-
quent disubstitution (Scheme 4). By using 20 mL ethyl acetate,
Figure 2. Telomerisation reaction in a high pressure batch reactor. The reac-
tion was performed at 808C with 25 mmol isosorbide, 16 mL 1,3-butadiene,
0.2 mol% palladium, 0.8 mol% TPPTS, and 4 mL water (0.5 mmol NaOH).
The picture was taken after 30 min reaction.
Scheme 4. Telomerisation of isosorbide under biphasic conditions.
ratio was significantly improved in favour of 2 by using 4 mL
of water (Table 4, entries 1 and 2). This solvent effect on the se-
lectivity was a valuable tool to synthesize 3 more selectively,
and a complementary study that involved organic solvents in
place of water was therefore conducted. For that purpose,
DMSO and tBuOH were suitable polar solvents as they also
contributed to the solubilisation of the catalyst in the isosor-
bide phase.
the reaction turned out to be extremely slow, as 90 h were
needed to reach a complete conversion of isosorbide. As ex-
pected, the diol was essentially converted into monoethers 2
and 3 and a mono/di ratio of 30 was obtained. High selectivi-
ties in monoethers were also obtained if the reaction was per-
formed with 4 mL of water. In that case, the reaction rate
turned out to be much higher, and a complete conversion of
isosorbide was attained after only 3 h. Surprisingly, although
the aqueous catalytic phase was expected to be less prone to
solubilise 1,3-butadiene, the reaction rate was not as greatly
impeded as in the former case (reaction performed with 20 mL
ethyl acetate).
Table 4. Telomerisation reaction of 1,3-butadiene with isosorbide cata-
lysed by [Pd(OAc)2]/4 TPPTS in organic and aqueous solvents.[a]
Entry
Solvent
[mL]
Conversion[b]
of 1 [%]
Selectivity[b] [%]
3/2
2
3
4
It thus appears that the dilution of 1,3-butadiene in an or-
ganic cosolvent results in a reduced concentration of 1,3-buta-
diene in the water/isosorbide phase, which is responsible for
limited reaction rates. This is also in agreement with the lower
rates obtained with an atmospheric gas pressure compared to
the batch experiments with initial loading of 1,3-butadiene;
the concentration of 1,3-butadiene in the catalytic phase is ex-
pected to be higher in the latter case.
1
2
3
4
5
6
7[c]
H2O (0.5)
H2O (4)
87
86
84
34
74
55
73
54
67
32
49
37
46
55
35
27
42
45
45
46
17
11
6
26
7
18
8
28
0.7
0.4
1.3
0.9
1.2
1
tBuOH (0.5)
tBuOH (4)
DMSO (0.5)
DMSO (4)
DMSO (0.5)
0.3
[a] The reactions were performed with 25 mmol isosorbide, 62.5 mmol
1,3-butadiene, 0.2 mol% palladium (vs isosorbide), 0.8 mol% TPPTS and
0.1 mmol LiOH at 808C for 2 h. [b] Conversions and selectivities were de-
termined by using GC analysis. [c] Reaction was performed with PPh3 in
place of TPPTS.
To confirm the presence of a liquid/liquid biphasic system,
the reaction was carried out in an autoclave equipped with
quartz windows. The experiment performed with 4 mL of
water clearly evidences the existence of two distinguishable
phases at 808C (Figure 2). The colourless upper phase, expect-
ed to be mainly composed of 1,3-butadiene at the beginning
of the reaction, remained almost constant in volume as 1,3-bu-
tadiene was converted and replaced by monoethers 2 and 3.
On the other hand, the yellowish water/isosorbide phase con-
taining the catalyst was concomitantly reduced in volume as
isosorbide was converted and the products were extracted to
the organic phase. After 2 h reaction at high conversion of iso-
sorbide, a black precipitate of palladium started to appear, and
the reaction medium became sluggish.
The telomerisation reactions performed by using 0.5 mL of
DMSO or tBuOH showed the formation of 3 as a major product
and the respective 3/2 ratios were 1.3 and 1.2. In more diluted
media (Table 4, entries 4 and 6), the conversions of isosorbide
turned out to be much lower, but the 3/2 ratios remained
higher than in water thus showing that the selectivity of the
reaction of 1 into 2 or 3 could be tuned, to some extent, by
changing the nature of the cosolvent. However, owing to the
more solubilising properties of organic solvents, it should be
noted that the overall yield of the monoethers was limited by
the formation of larger amounts of diether 4. In contrast to
water, organic solvents solubilise all the reactants in one
Interestingly, the addition of water also induced a variation
of the 3/2 ratio. The reaction with 0.5 mL of water as cosolvent
yielded predominantly the ethers 2 (ratio 3/2=0.7) and this
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M. Sauthier, V. Molinier et al.
unique phase thus hindering the beneficial biphasic effect for
the selective synthesis of monoethers at high isosorbide con-
versions (cf. entries 5 and 3 with entry 1 in Table 4). However,
crude products of reactions performed with DMSO and en-
riched with 3 were used for purification to access pure 3a.
Moreover, these solvents can be of interest elsewhere as they
are compatible with the use of neutral, cheaper, and less sensi-
tive triarylphosphines. By using PPh3 in place of the TPPTS and
with DMSO as solvent, the reaction showed similar conversions
of isosorbide, but large amounts of diether 4 were formed (see
entry 7). In addition, the selectivity was greatly improved in
favour of the monotelomer 2 and a low 3/2 ratio of 0.3 was
obtained.
rivatives 5a and 7a were obtained as the main reaction prod-
ucts. The measured conversions after two hours reaction were
similar in both cases, and this similarity in reactivity was con-
firmed by using a competitive reaction performed with equi-
molar amounts of isomannide and isoidide. Isomannide
showed a much larger reactivity compared to isoidide, if the
reaction was performed in DMSO instead of water. This is in
agreement with the improved reactivity of the endo-hydroxy
group of isosorbide versus the exo-hydroxy group when the
reaction was performed in DMSO instead of water. The endo-
hydroxy groups of isosorbide and isomannide are sterically
more crowded than the exo-2-hydroxy groups of isosorbide
and isoidide. However, endo-hydroxy groups are in general
more reactive. This higher reactivity is generally attributed to
the enhanced acidity of this site, due to the presence of a hy-
drogen bond with an oxygen atom of the adjacent cycle
(Scheme 3),[10a,12] associated with an enhanced deprotonation
of the endo-hydroxy group, due to the formation of chelates in
the presence of alkaline cations.[13] However, exceptions have
been reported, in particular in the case of the esterification of
isosorbide with acids under phase-transfer catalysed condi-
tions[14] as well as alkylation reactions performed in water.[13] In
these cases, water was indeed thought to, at least partially,
break the intramolecular hydrogen bonding, thus sterically
controlling the reactivity of the hydroxy groups. As a result,
the 2-regioisomer becomes the major product under these
conditions.
Isoidide and isomannide are C2-symmetric isomers of isosor-
bide with two exo and two sterically shielded and hydrogen-
bonded endo hydroxy groups (Scheme 3), respectively. These
compounds were further efficiently used as telogens in the te-
lomerisation reaction of 1,3-butadiene (Scheme 5).
Conclusions
The telomerisation reaction efficiently allows the synthesis of
isosorbide-based mono- or diethers with good yields. The
choice of the reaction conditions used for the synthesis is im-
portant to improve reaction rates and to tune the product dis-
tributions. Simple bases used in catalytic amounts allow higher
reaction rates compared to neat water as well as the synthesis
of diethers as the main reaction products. Biphasic conditions
that involve a sufficient amount of water are preferentially ap-
plied for higher selectivity towards monoethers. Under such re-
action conditions, the 2-O-octadienyl monoethers are the main
products. Switching from an aqueous to an organic medium
accesses the 5-O-octadienyl monoether as the major reaction
product, however the overall selectivity for monoethers is less
pronounced. The reaction can be applied to the selective syn-
thesis of monoethers derived from isomannide and isoidide
with water as the reaction solvent. Competitive reactions be-
tween isomannide and isoidide in water or DMSO evidence
the improved reactivity of exo-hydroxy groups in aqueous
media.
Scheme 5. Products from the telomerisation reaction of isomannide and isoi-
dide with 1,3-butadiene.
Both diols were selectively converted into octadienyl mono-
ethers 5a–b and 7a–b under biphasic aqueous reaction condi-
tions (Table 5, entries 1 and 2). Similar to isosorbide, linear de-
Table 5. Telomerisation reaction of 1,3-butadiene with isomannide and
isoidide catalysed by [Pd(OAc)2]/4 TPPTS in DMSO and water.[a]
Entry
Solvent Substrate
[4 mL]
Conversion[b]
[%]
Selectivity[b] [%]
Monoethers Diethers
1
2
H2O
H2O
Isomannide 60
>99
>99
98
97
83
<1
<1
<2
3
17
4
Isoidide
57
Isomannide 45
Isoidide 58
Isomannide 65
Isoidide 19
3
4
H2O
DMSO
Experimental Section
96
[a] The reactions were performed with 12.5 mmol isomannide and
12.5 mmol isoidide for the mixture entries 3 and 4, 25 mmol substrate for
entries 1 and 2, 62.5 mmol 1,3-butadiene, 0.2% palladium, 0.8% TPPTS,
and 0.1 mmol LiOH at 808C for 2 h. [b] Conversions and selectivities were
determined by using GC analysis.
Apparatus: NMR spectra were recorded on a Bruker AC 300 spec-
trometer (1H: 300 MHz, 13C: 75.5 MHz) and referenced to TMS. GC
analyses were carried out on a Chrompack CP 9002 apparatus
equipped with a flame ionisation detector and a CP-Sil 5CB
column using 100% dimethylpolysiloxane as internal phase (25 m
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ChemSusChem 2011, 4, 1104 – 1111

Synthesis of Amphiphilic Monoethers
length, 0.32 mm id). Undecane was chosen as internal standard for
GC analysis. The response factors of the major compounds toward
the internal standard were experimentally established. All experi-
ments were performed under a nitrogen atmosphere by using
standard Schlenk techniques. Experiments conducted under batch
conditions were carried out in a 100 mL stainless steel autoclave
with butadiene introduced in liquid form at low temperatures at
the beginning of the reaction. Semi-batch reactions were per-
formed in a 50 mL glass reactor connected to a butadiene cylinder
through a backpressure regulator to keep the butadiene pressure
constant. A rubber septum connected to the reactor allowed to
take aliquot samples during the reaction, which were analyzed by
GC.
2a: 1H NMR (300 MHz, CDCl3): d=5.72 (ddt, 1H, 3J(H,H)=17.2 Hz,
3J(H,H)=10.6 Hz, 3J(H,H)=6.5 Hz, CH2ÀCH=CH2), 5.64 (dt, 1H,
3
3J(H,H)=15.5 Hz, J(H,H)=7.5 Hz, CH2ÀCH=CHÀCH2O), 5.46 (dt, 1H,
3J(H,H)=15.5 Hz, 3J(H,H)=6.8 Hz, CH=CHÀCH2O), 4.93 (d, 1H,
3
3J(H,H)=17.2 Hz, CH=CH2), 4.88 (d, 1H, J(H,H)=10.6 Hz, CH=CH2),
4.53 (dd, 1H, 3J(H,H)=4.6 Hz, 3J(H,H)=4.9 Hz, H4 isosorbide), 4.39
(d, 1H, 3J(H,H)=4.6 Hz, H3 isosorbide), 4.19 (dddd, 1H, 3J(H,H)=
7.1 Hz, 3J(H,H)=5.9 Hz, 3J(H,H)=5.1 Hz, 3J(H,H)=4.9 Hz, H5 isosor-
bide), 3.98 (d, 1H, 3J(H,H)=4.2 Hz, H2 isosorbide), 3.95 (d, 1H,
2J(H,H)=10.3 Hz, 3J(H,H)=4.2 Hz, H1 isosorbide), 3.92 (d, 2H,
3J(H,H)=6.8 Hz, CH=CHÀCH2O), 3.81 (dd, 1H, 2J(H,H)=10.3 Hz,
3J(H,H)=3.9 Hz, H1 isosorbide), 3.77 (dd, 1H, 2J(H,H)=9.2 Hz,
3J(H,H)=5.1 Hz, H6 isosorbide), 3.47 (dd, 1H, 2J(H,H)=9.2 Hz,
3J(H,H)=5.9 Hz, H6 isosorbide), 2.84 (d, 1H, 3J(H,H)=7.1 Hz, OH),
1.99 (m, 4H, CHÀCH2ÀCH2ÀCH2ÀCH), 1.41 ppm (tt, 2H, 3J(H,H)=
7.5 Hz and 3J(H,H)=7.5 Hz, CH2ÀCH2ÀCH2); 13C NMR (75 MHz,
CDCl3): d=138.5 (1C, CH=CH2), 135.1 (1C, CH=CH-CH2O), 125.9
(1C, CH=CHÀCH2O), 114.7 (1C, CH=CH2), 86.0 (1C, C3 isosorbide),
83.1 (1C, C2 isosorbide), 81.8 (1C, C4 isosorbide), 73.5 (1C, C1 isosor-
bide), 73.3 (1C, C6 isosorbide), 72.3 (1C, C5 isosorbide), 70.4 (1C,
CH=CHÀCH2O), 33.2 (1C, CH2ÀCH=CH-CH2O), 31.7 (1 C, CH2ÀCH=
CH2), 28.2 ppm (1C, CH2ÀCH2ÀCH2).
Experimental procedure for telomerisation with atmospheric pres-
sure of 1,3-butadiene: The catalyst [Pd(OAc)2] (11.2 mg, 0.05 mmol),
the TPPTS (114 mg, 0.2 mmol), and isosorbide (3.65 g, 25 mmol)
were introduced in a glass reactor and flushed under nitrogen. An
aqueous soda solution (1m, 0.5 mL) was degassed and then added
to the powders. The reactor was flushed with nitrogen, put under
vacuum and filled with 1 bar of butadiene. The reactor was then
heated to 808C and magnetically stirred while the pressure of the
atmosphere of butadiene was kept constant by means of a back-
pressure regulator (butadiene being introduced in the gas phase)
during the overall experiment. During the reaction, the solution re-
mained purely homogeneous, and the kinetics was followed by
using GC analysis.
3a: 1H NMR (300 MHz, CDCl3): d=5.71 (ddt, 1H, 3J(H,H)=17.3 Hz,
3J(H,H)=10.2 Hz, 3J(H,H)=6.9 Hz, CH2-CH=CH2), 5.64 (dt, 1H,
3
3J(H,H)=15.3 Hz, J(H,H)=6.4 Hz, CH2ÀCH=CHÀCH2O), 5.49 (dt, 1H,
3J(H,H)=15.3 Hz, 3J(H,H)=6.4 Hz, CH=CHÀCH2O), 4.92 (d, 1H,
3J(H,H)=17.3 Hz, CH=CH2), 4.87 (d, 1H 3J(H,H)=10.2 Hz, CH=CH2),
4.57 (t, 1H, 3J(H,H)=4.2 Hz, H4 isosorbide), 4.33 (d, 1H, 3J(H,H)=
4.2 Hz, H3 isosorbide), 4.19 (m, 1H, H2 isosorbide), 3.78–4.12 (m,
5H, H5 isosorbide, H6 isosorbide, H1 isosorbide, CHÀCH2O), 3.96 (dd,
1H, 3J(H,H)=11.6 Hz, 3J(H,H)=6.5 Hz, CHÀCH2O), 3.45 (t, 1H,
3J(H,H)=8.5 Hz, H6 isosorbide), 3.38 (m, 1H, OH), 1.93 (m, 4H, CHÀ
CH2ÀCH2ÀCH2ÀCH), 1.35 ppm (m, 2H, 3J(H,H)=7.4 and 3J(H,H)=
7.4 Hz, CH2-CH2-CH2); 13C NMR (75 MHz, CDCl3): d=138.3 (1C, CH2À
CH=CH2), 135.1 (1C, CH2ÀCH=CH2O), 126.0 (1C, CH=CHÀCH2O),
114.6 (1C, CH=CH2), 88.1 (1C, C3 isosorbide), 79.9 (1C, C4 isosor-
bide), 78.9 (1C, C5 isosorbide), 76.2 (1C, C2 isosorbide), 75.1 (1C, C1
isosorbide), 71.2 (1C, CHÀCH2O), 69,7 (1C, C6 isosorbide), 33.1 (1C,
CH2ÀCH2ÀCH=CH2O), 31.5 (1C, CH2ÀCH2ÀCH=CH2), 28.0 ppm (1C,
CH2ÀCH2ÀCH2).
Experimental procedure for the telomerisation of 1,3-butadiene in
the autoclave: In a typical telomerisation experiment, the catalyst
[Pd(OAc)2] (11.2 mg, 0.05 mmol), the phosphine ligand (114 mg,
0.2 mmol) and isosorbide (3.65 g, 25 mmol) were introduced in a
100 mL stainless steel autoclave, which was bolted and flushed
with nitrogen. The base was dissolved in distilled water, degassed
under nitrogen flow, and then transferred into the autoclave. The
latter was cooled down to À208C. A precise volume of butadiene
was condensed in a Schlenk tube with an acetone–dry ice mixture
and transferred into the autoclave. Finally, the reactor was heated
to the chosen temperature and vigorously stirred (at a rate of
about 1000 rpm) with a magnetic stirrer for 2 h. After the reaction,
the system was cooled and excess gaseous butadiene was vented.
The crude product was homogenized by methanol addition, and
0.250 mL of undecane was added. Conversion and selectivities
were calculated from the GC analysis of the homogeneous mix-
ture.
1
3
4aa: H NMR (300 MHz, CDCl3): d=5.79 (ddt, 2H, J(H,H)=17.6 Hz,
3J(H,H)=10.3 Hz, 3J(H,H)=6.4 Hz, CH2ÀCH=CH2), 5.70 (dt, 2H,
3J(H,H)=15.3 Hz, J(H,H)=6.5 Hz, CH2ÀCH=CHÀCH2O-C2 isosorbide),
3
3
3
5.58 (dt, 1H, J(H,H)=15.3 Hz, J(H,H)=6.2 Hz, CH2ÀCH=CHÀCH2OÀ
3
3
C5 isosorbide), 5.52 (dt, 1H, J(H,H)=15,3 Hz, J(H,H)=6,2 Hz,), 4.99
(d, 2H, 3J(H,H)=17.6 Hz, CH=CH2), 4.95 (d, 2H, 3J(H,H)=10,3 Hz,
CH=CH2), 4.60 (t, 1H, 3J(H,H)=4.4 Hz, H4 isosorbide), 4.50 (d, 1H,
3J(H,H)=4.4 Hz, H3 isosorbide), 4.14 (dd, 1H, 3J(H,H)=11.7 Hz,
3J(H,H)=6.2 Hz, CHÀCH2OÀC2 isosorbide), 4.07–3.84 (m, 8H, H2 iso-
sorbide, H1 isosorbide, H5 isosorbide, 1 H6 isosorbide, 1H CHÀ
Separation of the telomers: 20 mL of water were added to the
slurry and the aqueous phase containing isosorbide, and the cata-
lyst was extracted by using acetate (3ꢂ20 mL). The organic phase
was dried by using Na2SO4 and evaporated. Telomers were then
partially separated by distillation under low pressure (4.10À2 mbar).
The distillation separated the two fractions containing mainly mon-
otelomers (108–1168C: 72% 2, 13% 3; 132–1458C: 17% 2, 65% 3)
and one fraction essentially consisting of the ditelomer (161–
1708C: 73% 4).
3
CH2OÀC2 isosorbide, CHÀCH2OÀC5 isosorbide), 3.57 (t, 1H, J(H,H)=
8.2 Hz, H6 isosorbide), 2.05 (m, 8H, CHÀCH2ÀCH2ÀCH2ÀCH),
1.48 ppm (tt, 4H, 3J(H,H)=7.4 Hz and 3J(H,H)=7.4 Hz, CH2ÀCH2À
CH2); 13C NMR (75 MHz, CDCl3): d=138.5 (2C, CH2ÀCH=CH2), 135.1
(1C, CH2ÀCH=CHÀCH2OÀC5 isosorbide), 134.9 (1C, CH2ÀCH=CHÀ
CH2OÀC2 isosorbide), 126.3 (1C, C8 CH=CH-CH2OÀC2 isosorbide),
126.0 (1C, C16 CH=CHÀCH2OÀC5 isosorbide), 114.7 (2C, CH=CH2),
86.4 (1C, C3 isosorbide), 83.5 (1C, C2 isosorbide), 80.1 (1C, C4 isosor-
bide), 79.1 (1C, C5 isosorbide), 73.4 (1C, C1 isosorbide), 71.3 (1C,
CHÀCH2OÀC5 isosorbide), 70.3 (1C, CHÀCH2OÀC2 isosorbide), 69.7
(1C, C6 isosorbide), 33.2 (2C, CH2ÀCH2ÀCH=CHÀCH2O), 31.7 (2C,
CH2ÀCH2ÀCH=CH2), 28.2 ppm (2C, CH2ÀCH2ÀCH2)
Pure 2a, 3a, and 4aa were obtained by purification of the en-
riched distillation fractions by using silica-gel column chromatogra-
phy with petroleum ether/ethyl acetate (80/20) as the eluent. How-
ever, 3a was best purified from the crude product in a reaction
performed in DMSO.
Pure monoethers of isomannide and isoidide were obtained by ex-
traction with ethyl acetate of the biphasic aqueous reaction and
further purified by using silica-gel column chromatography in the
same way as for the telomers of isosorbide.
5a: 1H NMR (300 MHz, CDCl3): d=5.80 (ddt, 1H, 3J(H,H)=17.8 Hz,
3J(H,H)=10.7 Hz, 3J(H,H)=6.5 Hz, CH2ÀCH=CH2), 5.74 (dt, 1H,
ChemSusChem 2011, 4, 1104 – 1111
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
1109

M. Sauthier, V. Molinier et al.
3J(H,H)=15.2 Hz, J(H,H)=6.5 Hz, CH2ÀCH=CHÀCH2O), 5.59 (dt, 1H,
3
Acknowledgements
3J(H,H)=15.2 Hz, 3J(H,H)=6.5 Hz, CH=CHÀCH2O), 5.01 (d, 1H,
3
3J(H,H)=17.8 Hz, CH=CH2), 4.96 (d, 1H, J(H,H)=10.7 Hz, CH=CH2),
This work was financially supported by the CPER, and we are
grateful to the Region Nord Pas de Calais, the Prꢀfecture de la
Region Nord-Pas-de-Calais, and the FEDER. We are also grateful
to the region Nord-Pas-de-Calais and the CNRS for J.L. and S.B.’s
Fellowships. R.F. gratefully acknowledges the financial support
from the BIOHUB program (http://www.biohub.fr).
4.52 (m, 2H, H4, H3 isomannide), 4.28 (q, 1H, 3J(H,H)=5.8 Hz, H5 iso-
mannide), 4.16 (dd, 1H, 3J(H,H)=5.8 Hz, CHÀCH2O), 4.12–3.95 (m,
4H, H2, H6, H1 isomannide and CHÀCH2O), 3.71 (m, 2H, H1, H6 iso-
mannide), 2.81 (s, 1H, OH), 2.07 (dd, 4H, 3J(H,H)=6.5 Hz and
3
3J(H,H)=7.5 Hz, CHÀCH2ÀCH2ÀCH2ÀCH), 1.49 ppm (tt, 2H, J(H,H)=
3
7.5 Hz and J(H,H)=7.5 Hz, CH2ÀCH2ÀCH2).
13C NMR (75 MHz, CDCl3): d=138.7 (1C, CH=CH2), 135.5 (1C, CH=
CHÀCH2O), 126.3 (1C, CH=CHÀCH2O), 114.8 (1C, CH=CH2), 82.0 (1C,
C4 isomannide), 80.8 (1C, C3 isomannide), 79.1 (1C, C2 isomannide),
75.1 (1C, C6 isomannide), 72.5 (1C, C5 isomannide), 71.7 (1C, CH=
CHÀCH2O), 71.4 (1C, C1 isomannide), 33.4 (1C, CH2ÀCH=CHÀCH2O),
31.8 (1C, CH2ÀCH=CH2), 28.3 ppm (1C, CH2ÀCH2ÀCH2).
Keywords: biomass · homogeneous catalysis · palladium ·
selectivity · telomerisation
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3J(H,H)=15.8 Hz, 3J(H,H)=6.8 Hz, CH=CHÀCH2O), 5.00 (d, 2H,
3
3J(H,H)=17.5 Hz, CH=CH2), 4.95 (d, 2H, J(H,H)=10.4 Hz, CH=CH2),
4.52 (m, 2H, H3 isomannide), 4.16–3.94 (m, 8H, CHÀCH2O, H2 iso-
3
mannide, H1 isomannide), 3.61 (t, 2H, J(H,H)=11.3 Hz, H1 isoman-
3
3
nide), 2.05 (dd, 8H, J(H,H)=6.8 Hz and J(H,H)=7.5 Hz, CHÀCH2À
CH2ÀCH2ÀCH), 1.47 ppm (tt, 4H, 3J(H,H)=7.5 Hz and 3J(H,H)=
7.5 Hz, CH2ÀCH2ÀCH2); 13C NMR (75 MHz, CDCl3): d=138.6 (2C,
CH=CH2), 135.1 (2C, CH=CHÀCH2O), 126.3 (2C, CH=CHÀCH2O),
114.7 (2C, CH=CH2), 80.3 (2C, C3 isomannide), 79.4 (2C, C2 isoman-
nide), 71.5 (2C, CH=CHÀCH2O), 71.0 (2C, C1 isomannide), 33.2 (2C,
CH2ÀCH=CHÀCH2O), 31.6 (2C, CH2ÀCH=CH2), 28.1 ppm (2C, CH2À
CH2ÀCH2).
7a: 1H NMR (300 MHz, CDCl3): d=5.81 (ddt, 1H, 3J(H,H)=17.1 Hz,
3J(H,H)=10.3 Hz, 3J(H,H)=6.5 Hz, CH2ÀCH=CH2), 5.72 (dt, 1H,
3
3J(H,H)=15.3 Hz, J(H,H)=6.5 Hz, CH2ÀCH=CHÀCH2O), 5.54 (dt, 1H,
3J(H,H)=15.3 Hz, 3J(H,H)=6.5 Hz, CH=CHÀCH2O), 5.01 (d, 1H,
3
3J(H,H)=17.1 Hz, CH=CH2), 4.96 (d, 1H, J(H,H)=10.3 Hz, CH=CH2),
4.68 (d, 1H, 3J(H,H)=4.0 Hz, H3 isoidide), 4.53 (d, 1H, 3J(H,H)=
4.0 Hz, H4 isoidide), 4.32 (m, 1H, H5 isoidide), 4.00 (m, 3H, H2 isoi-
dide, and CHÀCH2O), 3.84 (m, 4H, H1, H6 isoidide), 2.34 (s, 1H, OH),
2.07 (dd, 4H, 3J(H,H)=7.5 Hz and 3J(H,H)=6.5 Hz, CHÀCH2ÀCH2À
CH2ÀCH), 1.49 ppm (tt, 2H, 3J(H,H)=7.5 Hz and 3J(H,H)=7.5 Hz,
CH2ÀCH2ÀCH2); 13C NMR (75 MHz, CDCl3): d=138.7 (1C, CH=CH2),
135.3 (1C, CH=CHÀCH2O), 126.0 (1C, CH=CHÀCH2O), 114.8 (1C,
CH=CH2), 87.3 (1C, C4 isoidide), 85.4 (1C, C3 isoidide), 82.7 (1C, C2
isoidide), 76.2 (1C, C5 isoidide), 74.5 (1C, C6 isoidide), 72.6 (1C, C1
isoidide), 70.6 (1C, CH=CHÀCH2O), 33.4 (1C, CH2ÀCH=CHÀCH2O),
31.8 (1C, CH2ÀCH=CH2), 28.3 ppm (1C, CH2ÀCH2ÀCH2).
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8a: 1H NMR (300 MHz, CDCl3): d=5.80 (ddt, 2H, 3J(H,H)=17.4 Hz,
3J(H,H)=10.6 Hz, 3J(H,H)=6.8 Hz, CH2ÀCH=CH2), 5.71 (dt, 2H,
3
3J(H,H)=15.4 Hz, J(H,H)=6.8 Hz, CH2ÀCH=CHÀCH2O), 5.54 (dt, 2H,
3J(H,H)=15.4 Hz, 3J(H,H)=6.8 Hz, CH=CHÀCH2O), 5.01 (d, 2H,
3
3J(H,H)=17.4 Hz, CH=CH2), 4.96 (d, 2H, J(H,H)=10.6 Hz, CH=CH2),
4.62 (s, 2H, H3 isoidide), 4.00 (m, 4H, H2 isoidide and CHÀCH2O),
3.84 (m, 4H, H1 isoidide), 2.06 (dd, 8H, 3J(H,H)=7.5 Hz and
3
3J(H,H)=6.8 Hz, CHÀCH2ÀCH2ÀCH2ÀCH), 1.49 ppm (tt, 4H, J(H,H)=
7.5 Hz and 3J(H,H)=7.5 Hz, CH2ÀCH2ÀCH2); 13C NMR (75 MHz,
CDCl3): d=138.6 (2C, CH=CH2), 135.0 (2C, CH=CHÀCH2O), 125.9
(2C, CH=CHÀCH2O), 114.7 (2C, CH=CH2), 85.4 (2C, C3 isoidide), 82.5
(2C, C2 isoidide), 72.3 (2C, C1 isoidide), 70.4 (2C, CH=CHÀCH2O),
33.2 (2C, CH2ÀCH=CHÀCH2O), 31.7 (2C, CH2ÀCH=CH2), 28.1 ppm
(2C, CH2ÀCH2ÀCH2).
1110
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ChemSusChem 2011, 4, 1104 – 1111

Synthesis of Amphiphilic Monoethers
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Received: March 9, 2011
Published online on July 15, 2011
ChemSusChem 2011, 4, 1104 – 1111
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
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