Exceptional efficiency of palladium nanoparticle catalyzed Heck cross-coupling in binary task specific ionic liquids

Article abstract of DOI:10.1016/j.crci.2010.07.001

The utilization of the task specific onium salt supported substrates in ionic liquids as solvents (i.e., binary task specific ionic liquids) for palladium nanoparticle catalyzed Heck cross-coupling reactions is presented. Adequate substrates have been prepared and used leading to expected products in very high yields. Exceptionally high turnover (TON = 940,000, TOF = 208,000) can be achieved taking advantages of this combination. Additional advantages of this technology reside in the monitoring of the reaction and purification of products after degrafting which are simplified to the extreme.

Full text of DOI:10.1016/j.crci.2010.07.001

C. R. Chimie 14 (2011) 671–679
Contents lists available at ScienceDirect
Comptes Rendus Chimie
www.sciencedirect.com
Preliminary communication/Communication
Exceptional efficiency of palladium nanoparticle catalyzed Heck
cross-coupling in binary task specific ionic liquids
*
Fatima Hassine, Mathieu Pucheault, Michel Vaultier
UMR CNRS 6510, campus de Beaulieu, universite´ de Rennes 1, 263, avenue du Ge´ne´ral-Leclerc, 35042 Rennes, France
A R T I C L E I N F O
A B S T R A C T
Article history:
The utilization of the task specific onium salt supported substrates in ionic liquids as
solvents (i.e., binary task specific ionic liquids) for palladium nanoparticle catalyzed Heck
cross-coupling reactions is presented. Adequate substrates have been prepared and used
leading to expected products in very high yields. Exceptionally high turnover
(TON = 940,000, TOF = 208,000) can be achieved taking advantages of this combination.
Additional advantages of this technology reside in the monitoring of the reaction and
purification of products after degrafting which are simplified to the extreme.
Received 1 April 2010
Accepted after revision 6 July 2010
Available online 27 April 2011
Keywords:
Homogeneous catalysis
Ionic liquids
´
ß 2011 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Heck reaction
1. Introduction
[10], or oligonucleotides [11]. Despite their success,
multimeric soluble systems still have drawbacks limiting
Since the 1960s, solid phase supported organic synthe-
sis has proven to be one of the best systems for synthesis of
libraries of compounds in a short period of time [1]. Phase
discrepancy is allowing drastic simplification in purifica-
tion and, despite the addition of large excesses of reagents
usually used to drive reactions to completion, only
filtration and washes are often necessary to obtain
products with good purities. However, some limitations
remain to this appealing technology, including low loading
capacity and poor kinetics. Indeed, the heterogeneous
nature of mixture is slowing down reactions due to poor
diffusion of reagents and/or difficulties in accessing the
reaction site on the resin. Moreover, monitoring reactions
is somehow tricky and can require special analysis
techniques such as HR MAS NMR. As an answer to this
drawback, some systems have been developed in solution
phase. If perfluorous systems are efficient in multiphasic
reactions [2–4], other approaches using dendrimeric
alcohols [5], soluble polystyrene [6–8], or polyethylene
glycols were successful as well. The last, for example have
been used for synthesizing peptides [9], oligosaccharides
their applicability. Indeed, low loading capacity (PEG 5000
has a 0.2 mmol.gÀ1 loading capacity, for example) along
with high water solubility prevent large scale use of PEG as
support in synthesis. Furthermore, reagents and side
products often co-precipitate during the purification step
leading to impure products after cleavage.
An alternative to these systems has arisen recently from
the field of ionic liquids. Liquid below 100 8C, ionic liquids
consist only of ions conferring them a unique structure and
characteristics otherwise unattainable [12]. Besides their
extremely low vapor pressure, inflammability and thermal
stability, their physical and chemical properties can be
finely tuned by adjusting a volo the nature of the cation
and the anion. Indeed, by grafting a functional group to an
ionic core, one can administrate special chemical proper-
ties to an onium salt which can then serve as a reagent or
reactant. These so-called Task Specific Ionic Liquids (TSILs)
[13] possess all ionic liquid advantages and can be used as
templates for supported organic synthesis on onium salts
in solution [14,15]. Besides offering a nice alternative to
solid phase supported synthesis, advantages of these
soluble supports are numerous: reactions are carried out
under homogeneous phase, recovering liquid phase
kinetics;
a classical work-up would consist only in
* Corresponding author.
E-mail address: michel.vaultier@univ-rennes1.fr (M. Vaultier).
filtration and washing several times to remove excess
1631-0748/$ – see front matter ß 2011 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.crci.2010.07.001

672
F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
Table 1
reagent and side products; solubility properties of reagent
can be adjusted by changing the counterion; reactions are
easily monitored by simple 1H NMR experiments; these
supports have high loading capacity (4.87 mmol.gÀ1 for
[HO(CH2)3NMe3][BF4] for example). Moreover, if they are
not liquid at room temperature or slightly above, due, for
example, to functionalization which increases their
melting point, they can be used as solutions in molecular
solvents or ionic liquids. These binary task specific ionic
liquids have already been successfully used for the
synthesis of numerous species [13,16]. Some representa-
tive examples include peptides synthesis [17], radical
reactions [18], multicomponent reactions [19–21], bio-
chemical transformations [22–27] and transition metal
catalyzed reactions [28–30]. The last are particularly
interesting in the sense that ionic liquids have already
been shown to be good solvents for Heck reactions [31–34]
for multiple reasons [35–41]. Indeed, the ionic nature of
the solvent naturally favors dissolution and capture of
catalyst in the ionic liquid phase which can be recycled
with or without supporting a ligand [42,43]. It also
accelerates considerably kinetic rates by in situ formation
of NHC-carbene ligands when using imidazolium salts
[44].
Supported acrylates prepared following Scheme 1 synthesis.
Entry A+
n
XÀ
Product Yielda (%)
À
1
2
Imidazolium
1
1
1
1
0
2
4
1
1
1
NTf2À 6a1
85
80
77
98
90
77
78
98
93
90
Pyridinium
NTf2 4a1
3
Tri(n-butyl)phosphonium
Trimethylammonium
Trimethylammonium
Trimethylammonium
Trimethylammonium
Trimethylammonium
Trimethylammonium
Trimethylammonium
NTf2À 5a1
NTf2À 3a1
NTf2À 3a0
NTf2À 3a2
4
5
6
7
NTf2
BrÀ
3a4
3b1
3c1
3d1
8
À
9
BF4À
10
PF6
a
Isolated yield after purification.
described afforded N,N-dimethyl-1-aminobutan-4-yl-4’-
iodobenzoate 9 in 88% yield. Quaternisation of tertiary
amine 9 led to supported iodobenzene 10xn bearing a
counteranion depending on the reagent used for methyla-
tion (triflate, iodide, methylsulfate). More diversity could
be introduced by a simple ion metathesis in water leading
to triflimide, hexafluorophosphate and tetrafluoroborate
analogs (Method A). After anion metathesis, halide content
turned out to be negligible as the silver nitrate test was
negative (Schemes 1 and 2, Table 2).
In this article, we would like to report the use of task
specific onium salts as soluble supports in Heck reactions.
Supporting either olefins or aryl halides has been envi-
sioned and used with a comparable success. Moreover, by
investigating low catalyst loading, we discovered how
[Pd(OAc)2] by reaction with [tmba][PF6] is forming
palladium nanoparticles leading to TON up to 106 and
2.2. Conditions optimization
Indeed, the Heck reaction has already been largely
studied in ionic liquids. This coupling reaction is particu-
larly well suited to ionic liquids physicochemical proper-
ties as it is favored by using polar solvents or in the
presence of ammonium salts [45] which stabilize Pd
complexes [46]. Preliminary experiments were conducted
in both ionic liquid and molecular solvents. In the presence
of 1% of [Pd(OAc)2] as a catalyst and potassium carbonate
as a base, supported olefin 3a1 reacts efficiently at 80 8C
with iodobenzene to afford cinnamate Ph-14a1. Quantita-
tive conversions were achieved in [tmba][NTf2] and
[emim][NTf2] after 2 h at 110 8C, but only 70% were
observed in acetonitrile. Furthermore E/Z selectivity was
highly superior in ionic liquids as only the (E)-isomer is
observed where 12% of the (Z)-compound was obtained in
CH3CN. Notably, supported acrylate is much more reactive
than the corresponding methyl ester as unsupported
acrylate underwent reaction with a poor 26% conversion
under the same conditions in acetonitrile (Scheme 3).
Like traditionally observed in the case of the Heck
reaction, increasing temperature is improving kinetics,
and either organic or mineral bases can alternatively be
TOF up to 2 Â 105 hÀ1
.
2. Results and discussion
2.1. Supports synthesis
First, onium salt supported acrylates were obtained via
coupling between acryloyl chloride 2 and
v-hydroxylated
onium salts 1. Interestingly, triethylamine, classically used
in this type of reaction was efficient but led to purification
difficulties of salts 3–6 which were bypassed by using
potassium carbonate instead followed by a simple filtra-
tion of mineral salts after reaction. Following this
procedure, 10 different supported acrylates
3 were
obtained in good yields (Table 1) with various cations
such as imidazolium (Entry 1, 6a1), pyridinium (Entry 2,
4a1), tributylphosphonium (Entry 3, 5a1) or trimethylam-
monium (Entry 4, 3a1). Chain spacing length can also be
modified from two to six carbons without notably affecting
yields (Entry 4–7). Similarly to triflimide, other anions can
be used in this reaction, such as bromide (Entry 8, 3b1),
tetrafluoroborate (Entry 9, 3c1) or hexaflurophosphate
(Entry 10, 3d1). In all cases, acrylates were obtained under
pure form with no remaining starting alcohol.
Eventually, one could envisage supporting the Heck
reaction via the iodoarenes instead of the acrylates.
Therefore, we decided to synthesize supported iodoben-
zene with the same sort of strategy. Benzoylation of N,N-
dimethyl-1-aminobutan-4-ol 7 with 4-iodo benzoyl chlo-
ride under the same reaction conditions as previously
Scheme 1. Preparation of onium salt supported acrylates.

F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
673
Scheme 2. Preparation of onium salt supported aryl iodides.
used although Et3N was found to accelerate reactions. An
attempt to diminish palladium concentration turned out
to be particularly interesting. Indeed, for practical
reasons, when using less than 100 ppm of Pd, simply
weighting palladium acetate on a precision scale is not
sufficiently satisfactory enough for loading accuracy. We
decided to dilute palladium acetate in an ionic matrix
whose melting point is above room temperature
[tmba][PF6] (m.p. = 156 8C). By simply heating above this
temperature a mixture of 0.1% [Pd(OAc)2] in [tmba][PF6]
under inert atmosphere, a grey powder Pd-CAT was
obtained after cooling which can be used directly to
catalyze Heck reactions. This powder Pd-CAT is composed
of palladium nanoparticles (4 nm) probably responsible
corresponding to
a
TON of 9.4 Â 105 and
a
TOF of
2 Â 105 hÀ1. These results are particularly significant for
ligandless palladium catalysis as only few examples [47]
are available in the literature with catalytic loading
reaching below 10 ppm, even using a specially designed
ligand (Scheme 4).
Similarly, supported iodobenzene was tested in Heck
reaction with acrylates. To our delight, the reaction is
equally efficient and cinnamic esters are isolated in good
yields after only 10 min at 110 8C using 0.1% Pd-CAT.
Catalyst loading diminution was also investigated in this
case, and using 10 ppm of Pd-CAT in the same conditions
as previously described, quantitative conversion was
achieved after a short 90-min period. However, attempts
to use only 1 ppm of palladium turned out to be less
successful as only 35% conversion was reached after 12 h
where 99% were attained using 3a1 under the very same
conditions. Transesterification of the crude cinnamic ester
Ph-14a1 in boiling methanol in the presence of traces of
HCl gave quantitatively the methyl trans cinnamic ester
after removal of excess of MeOH under vacuum and
extraction with ether in an excellent state of purity > 99%,
as indicated by GC/MS analysis. By using a two-carbon
chain onium salt support, the hydrolysis of cinamate
esters occurred during work-up. For linkers bearing more
than four carbons, the final transesterification was too
slow for practical applications. Three carbons turned out
to be the best compromise between reactivity and
stability.
for activity and larger aggregates (ꢀ10
mm) (Fig. 1).
Our best result was obtained using [tmba][PF6]
(m.p. = 156 8C) as a solvent: at 110 8C, using only 1 ppm
of Pd-CAT, 94% conversion was obtained after 270 min
Table 2
Supported aryl iodides prepared following Scheme 2 procedure.
Entry
Product
Method
Reagent
Yielda (%)
1
2
10e2
10h2
10f2
10a1
10d2
10c0
10c1
10c2
10c4
10d2
10g0
10g1
13b0
13c0
A
A
A
B
A
B
A
B
A
A
B
B
B
B
MeI
99
96
94
95
90
90
86
83
87
96
93
95
92
85
MeOTf
3
Me2SO4
LiNTf2
4
5
MeI then LiNTf2
HBF4
6
7
MeI then HBF4
HBF4
8
9
MeI then HBF4
MeI then HPF6
-
10
11
12
13
14
-
b
-
HBF4
a
Isolated yield from 7 or 11.
b
Bromide was used instead of 11.
Scheme 3. Mizoroki-Heck cross-coupling with supported acrylates.

674
F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
Scheme 4. Mizoroki-Heck cross-coupling using Pd-CAT.
ments. Interestingly, support counter anion showed great
influence on kinetics. Using 100 ppm of [Pd(OAc)2] in
[tmba][NTf2], the reaction was quantitative after 1 h with
10c2 (BF4) where lower conversion was observed for the
same time with another anion (PF6, 10d2, 93%; NTf2, 10a2,
93%; OTf, 10h2, 82%; MeSO4, 10f2, 41%; I, 10e2, 28%). Ester
15c1 could be transesterified under the conditions
described above to the corresponding methyl cinnamic
diester in very good yield. After transesterification, the
remaining Binary Task Specific Ionic Liquids could be
recycled several times without loss of matter beside other
than mechanical loss during solid transfer. Interestingly, if
the ppm level of palladium could not be reused, no side
reactions were observed even after several cycles.
Fig. 1. TEM picture of Pd-CAT.
2.3. Synthesis of a library of cinnamic esters
In order to validate our methodology for parallel
synthesis, we used this method to prepare a small library
Concerning use of supported iodobenzene, the reaction
was found to be much more efficient in ammonium salt
than in imidazolium based ionic liquids, probably due to
inhibition of the catalyst by formation of Pd-NHC
complexes [48]. However, this effect was only detectable
using less than 100 ppm of palladium, slowing down the
reaction enough to accurately perform kinetic experi-
of substituted acrylates. Hence, a mixture of nine
substituted iodobenzenes has been coupled with the
supported acrylate 3a1. Noteworthy, all conversions were
quantitative after 3 h in [tmba][NTf2]. Supported cinna-
mates were obtained with good purity as no (Z)-isomer
could be detected by 1H NMR (< 1%) (Table 3).
Table 3
Synthesis of a library of cinnamic esters.
Entry
Ar
Conv.a (%)
E/Z ratioa
1
2
3
4
5
6
7
8
9
Ph
100
100
100
100
100
100
100
100
100
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
99/1
2-MePh
3-MePh
4-MePh
1-Napth
2-NO2Ph
4-MeOPh
4-FPh
3-BrPh
a
Determined by 1H NMR.

F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
675
3. Conclusion
4.3. General procedure for anion metathesis with HPF6
(Procedure II)
We showed here that the onium salt supported
organic synthesis (OSSOS) strategy is highly versatile
and can also be used in combination with palladium
catalyzed reaction. Noteworthy, we found that a simple
catalyst, prepared from a mixture of a high melting point
onium salt and palladium acetate displays exceptional
activity as a ligandless catalyst [49]. Moreover, this
material, mostly composed of nanoparticles is a non-
hygroscopic, grey powder, stable at room temperature
under inert atmosphere.
To a solution of onium halide (0.1 mmol) in 15 mL of
water was added 0.15 mmol of an aqueous HPF6 solution
(60%). After 2 h at r.t., a solid has formed. Filtration and
washes (3 Â 10 mL Et2O) afforded analytically pure onium
hexafluorophosphate.
4.4. General procedure for anion metathesis with LiNTf2
(Procedure III)
To a solution of onium halide (0.1 mmol) in 10 mL of
water was added 0.11 mmol of an aqueous LiNTf2 solution
(10 mL). After 2 h at r.t., the aqueous phase was extracted
with 3 Â 15 mL of CH2Cl2. Organic fractions were combined
and concentrated under reduced pressure. To remove
remaining traces of water, the oil was dried under vacuum
(0.5 mmHg) at 60 8C for 2 h.
4. Experimental
4.1. General methods
All glassware was oven-dried prior to use and reactions
were run under an inert atmosphere of argon using
standard Schlenk techniques. Yields reported were from
isolated products and determined to be pure by GC (DB-5
4.5. General procedure for anion metathesis with HBF4
(Procedure IV)
column) or TLC (pre-coated plates of silica gel 60 F254
,
stained with a potassium permanganate solution), and
NMR spectroscopy. Solvents were carefully dried and
purified following known procedures prior to use [50]. All
other standard chemicals were purchased from Fisher,
Alfa Aesar or Aldrich Chemical Co. and used without
further purification. Reactions were monitored by gas
chromatography (GC-MS) (GC system: HP 6890 series,
Mass selective detector HP 5973) using a capillary column
DB-5MS. Column chromatography purifications were
To a solution of onium halide (0.1 mmol) in 15 mL of
water was added 0.15 mmol of an aqueous HBF4 solution
(50%). After 12 h at r.t., water was removed under reduced
pressure affording a white solid. The residue was filtered
and washed with 2 Â 15 mL Et2O affording analytically
pure onium tetrafluoroborate.
4.6. General procedure for Heck coupling with supported
acrylate (Procedure V)
performed on silica gel Si 60 (40–63
mm, 230–400 mesh,
Merck). Melting points were determined on an electro-
thermal IA9300 digital melting point instrument. NMR
A mixture of 3a1 (1.5 mmol), iodobenzene (839
mL,
spectra were recorded on
200.13 MHz, 13C: 50.32 MHz) or AC 300
300.13 MHz), 1H chemical shifts (
) are given with
a
Bruker ARX 200 (1H:
7.5 mmol, 5 eq), [Pd(OAc)2] (2.43 mg, 0.015 mmol, 1%), and
K2CO3 (331 mg, 2.25 mmol, 1.5 eq) in 2 mL of [tmba][NTf2]
or (DMF) was heated at 80 8C. Reaction was monitored by
1H NMR. After completion of the reaction, remaining
reactants were eliminated with washes using alternatively
water and Et2O.
P
(1H:
d
apparent multiplicities in ppm relative to TMS as external
standard, J values in Hz, 13C chemical shifts are given
relative to the central signal of CDCl3 at 77.0 ppm. IR
spectra were obtained on a Bio-Rad FTS 175C FT-IR
spectrophotometer. High resolution mass spectra mea-
surements were performed at the Centre regional de
mesures physiques de l’Ouest (CRMPO, University of
Rennes 1) using a Varian MAT 311 with BE geometry
(reversed Nier-Johnson) and EI athod or Micromass
ZABSpec TOF with EBE OA TOF geometry with LSIMS
ionization (liquid secondary ion mass spectrometry) at
8 kV with Cs+ gun in m-nitrobenzyl alcohol (mNBA).
4.7. General procedure for Heck coupling with supported
iodobenzoic acids (Procedure VI)
A mixture of 10a2 (1.5 mmol), olefin (7.5 mmol, 5 eq),
[Pd(OAc)2] (2.43 mg, 0.015 mmol, 1%), and K2CO3 (331 mg,
2.25 mmol, 1.5 eq) in 2 mL of [tmba][NTf2] (or DMF) was
heated at 80 8C. Reaction was monitored by 1H NMR; at the
end of the reaction, remaining reactants were eliminated
with washes using alternatively water and Et2O.
4.2. General procedure for supported acrylate synthesis
(Procedure I)
4.8. Onium salt supported products
To a solution of hydroxyl derivatized onium salt and
K2CO3 (5 eq) in acetonitrile (0.1 M) was added 3 eq. of
acylating agent. After 2 h at 80 8C, solvents and unreacted
acyl chloride were removed under vacuum. Product was
extracted with 3 Â 10 mL.mmolÀ1 CH2Cl2. Organic layers
were combined and concentrated under reduced pres-
sure to afford analytically pure onium salt supported
acrylate.
4.8.1. [AcrEtTMA][NTf2] 3a0 (2-acryolyloxyethyl)
trimethylammonium bistrifluoromethanesulfonamide
Following general procedure I using (2-hydroxyethyl)-
trimethylammonium
bistrifluoromethanesulfonamide
[HOEtTMA][NTf2] and acryloyl chloride, [AcrEtTMA][NTf2]
was obtained in 90% yield as a pink oil. 1H NMR (200 MHz,
acetone-d6):
d = 3.50(s, 9H), 4.03–4.40 (m, 2H), 4.73–4.85
(m, 2H), 6.05 (dd, 1H, J1 = 1.9 Hz, J2 = 10.5 Hz), 6.25 (dd, 1H,

676
F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
J1 = 10.5 Hz, J2 = 17.3 Hz), 6.45 (dd, 1H, J1 = 1.9 Hz,
J2 = 17.3 Hz). 13C (50 MHz, acetone-d6):
= 54.0 (t,
J = 4.2 Hz), 58.2, 65.2, 121.0 (q, JCF = 374 Hz), 128.8, 132.2,
165.5. LRMS(APCI): [C+] (C8 H16NO2) 158.3.
4.8.6. [AcrBuTMA][NTf2] 3a2 (6-acryolyloxybutyl)
trimethylammonium bistrifluoromethanesulfonamide
Following general procedure I using (4-hydroxybutyl)-
d
trimethylammonium
bistrifluoromethanesulfonamide
[HOBuTMA][NTf2] and acryloyl chloride, [AcrBuTMA]
4.8.2. [AcrPrTMA][Br] 3b1 (3-acryolyloxypropyl)
trimethylammonium bromide
[NTf2] 3a2 was obtained in 77% yield as a pale yellow oil.
1HNMR(200 MHz, acetone-d6):
d = 1.70–1.90(m, 2H), 2.00–
Following general procedure I using (3-hydropropyl)-
trimethylammonium bromide [HOPrTMA][Br] and acry-
loyl chloride, [AcrPrTMA][Br] was obtained in 98% yield as
2.20 (m, 2H), 3.40 (s, 9H), 3.58–3.72 (m, 2H), 4.25 (t, 2H,
J = 6.0 Hz), 5.80(dd, 1H, J1 = 1.9 Hz, J2 = 10.7 Hz), 6.05(dd, 1H,
J1 = 17.2 Hz, J2 = 10.7 Hz), 6.15 (dd, 1H, J1 = 1.9 Hz,
J2 = 17.2 Hz). 13C (50 MHz, acetone-d6):
d = 20.9, 26.4, 54.0,
a colorless oil. 1H NMR (200 MHz, acetone-d6):
d
= 2.15–
2.20 (m, 2H), 3.15 (s, 9H), 3.48–3.52 (m, 2H), 4.18 (t, 2H,
J = 6.0 Hz), 5.75 (dd, 1H, J1 = 1.9 Hz, J2 = 10.5 Hz), 6.15 (dd,
1H, J1 = 10.5 Hz, J2 = 17.3 Hz), 6.15 (dd, 1H, J1 = 1.9 Hz,
64.5, 67.4, 122.2 (q, JCF = 374 Hz), 129.7, 131.8, 167.0. HRMS
(FAB): [C+] (C10H20NO2). Calcd: 186.1494, found: 186.1506.
J2 = 17.3 Hz). 13C (50 MHz, acetone-d6):
d
= 21.7, 52.2 (t,
4.8.7. [AcrHexTMA][NTf2] 3a4 (6-acryolyloxyhexyl)
trimethylammonium bistrifluoromethanesulfonamide
Following general procedure I using (6-hydrohexyl)-
J = 4.2 Hz), 60.4 (t, J = 3.0 Hz), 62.6, 127.4, 130.6, 165.0.
HRMS(FAB): [C+] (C9H18NO2). Calcd: 172.1338, found:
172.1356.
trimethylammonium
bistrifluoromethanesulfonamide
[HOHexTMA][NTf2] and acryloyl chloride, [AcrHexT-
4.8.3. [AcrPrTMA][BF4] 3c1 (3-acryolyloxypropyl)
trimethylammonium tetrafluoroborate
MA][NTf2] 3a4 was obtained in 78% yield as a pale yellow
oil. 1H NMR (200 MHz, acetone-d6):
d = 1.40–1.60 (m, 4H),
Following general procedure I using (3-hydropropyl)-
trimethylammonium tetrafluoroborate [HOPrTMA][BF4]
and acryloyl chloride, [AcrPrTMA][BF4] was obtained in
93% yield as a white solid. 1H NMR (200 MHz, acetone-d6):
1.65–1.85 (m, 2H), 1.90–2.10 (m, 2H), 3.32 (s, 9H), 3.06–
3.15 (m, 2H), 4.52 (t, 2H, J = 6.4 Hz), 5.80 (dd, 1H, J1 = 2.1 Hz,
J2 = 10.1 Hz), 6.05 (dd, 1H, J1 = 17.2 Hz, J2 = 10.1 Hz), 6.15
(dd, 1H, J1 = 2.1 Hz, J2 = 17.2 Hz). 13C (50 MHz, acetone-d6):
d
= 2.28–3.31 (m, 2H), 3.32 (s, 9H), 3.06–3.15 (m, 2H), 4.52
d = 23.4, 26.1, 26.5, 26.5, 53.6, 64.8, 67.4, 121.0, 129.6,
(t, 2H, J = 6.6 Hz), 5.80 (dd, 1H, J1 = 1.9 Hz, J2 = 10.0 Hz),
6.05 (dd, 1H, J1 = 18.3 Hz, J2 = 10.0 Hz), 6.15 (dd, 1H,
J1 = 1.9 Hz, J2 = 18.3 Hz). 13C (50 MHz, acetone-d6):
131.1, 166.6.
4.8.8. [AcrPrTBP][NTf2] 5a1 (3-acryolyloxypropyl)
tributylphosphonium bistrifluoromethanesulfonamide
Following general procedure I using (3-hydropropyl)-
d
= 22.8; 53.3, 61.5, 63.8, 128.5, 131.7, 167.3. LRMS(APCI):
[2C+, BF4] 431.
tributylphosphonium
bistrifluoromethanesulfonamide
4.8.4. [AcrPrTMA][NTf2] 3a1 (3-acryolyloxypropyl)
[HOPrTBP][NTf2] and acryloyl chloride, [AcrPrTBP][NTf2]
was obtained in 77% yield as a pale yellow oil. 1H NMR
trimethylammonium bistrifluoromethanesulfonamide
Following general procedure I using (3-hydropropyl)-
trimethylammonium bistrifluoromethanesulfonamide
[HOPrTMA][NTf2] and acryloyl chloride, [AcrPrTMA]
[NTf2] was obtained in 90% yield as a pale yellow oil.
(200 MHz, acetone-d6):
d = 1.00 (t, 9H, J = 7.2 Hz), 1.45–
1.85 (m, 12H), 2.10–2.28 (m, 2H), 2.48–2.70 (m, 8H), 4.30
(t, 2H, J = 6.3 Hz), 5.58 (dd, 1H, J1 = 10.2 Hz, J2 = 1.9 Hz), 6.18
(dd, 1H, J1 = 17.2 Hz, J2 = 10.2 Hz), 6.40 (dd, 1H, J1 = 17.2 Hz,
J2 = 1.9 Hz). 13C (50 MHz, acetone-d6):
d = 13.1, 17.8, 18.8,
1H NMR (200 MHz, acetone-d6):
d
= 2.22–2.25 (m, 2H),
3.25 (s, 9H), 3.60–3.75 (m, 2H), 4.15 (t, 2H, J = 6.0 Hz),
5.80 (dd, 1H, J1 = 1.9 Hz, J2 = 10.7 Hz), 6.05 (dd, 1H,
J1 = 17.2 Hz, J2 = 10.7 Hz), 6.15 (dd, 1H, J1 = 1.9 Hz,
21.1, 23.4, 23.5, 23.9, 63.8, 121.1 (q, JCF = 374 Hz), 128.6,
131.1, 165.7.
J2 = 17.2 Hz). 13C (50 MHz, acetone-d6):
d
= 29.2, 54.2 (t,
4.8.9. [AcrPrPyr][NTf2] 4a1 (3-acryolyloxypropyl)pyridinium
bistrifluoromethanesulfonamide
JC-N = 4.0 Hz), 65.2, 65.2, 121.0 (q, JCF = 374 Hz), 129.4,
132.1, 165.6. 19F (282 MHz, acetone-d6): À79.8.
HRMS(FAB): [C+] (C9H18NO2). Calcd: 172.1338, found:
172.1346.
Following general procedure I using (3-hydropropyl)-
pyridinium
bistrifluoromethanesulfonamide
[HOPr-
Pyr][NTf2] and acryloyl chloride, [AcrPrPyr][NTf2] was
obtained in 80% yield as a pale yellow oil. 1H NMR
4.8.5. [AcrPrTMA][PF6] 3d1 (3-acryolyloxypropyl)
trimethylammonium hexafluorophosphate
(200 MHz, acetone-d6): d = 2.43–2.72 (m, 2H), 4.15 (t, 2H,
J = 5.8 Hz), 5.08 (t, 2H, J = 6.8 Hz), 5.90(dd, 1H, J1 = 10.3 Hz,
J2 = 2.0 Hz), 6.18 (dd, 1H, J1 = 17.0 Hz, J2 = 10.3 Hz), 6.40 (dd,
1H, J1 = 17.0 Hz, J2 = 2.0 Hz), 8.10 (t, 2H, J = 7.0 Hz), 8.52 (m,
Following general procedure I using (3-hydropropyl)-
trimethylammonium
MA][PF6] and acryloyl chloride, [AcrPrTMA][PF6] was
obtained in 90% yield as
white solid. 1H NMR
(200 MHz, acetone-d6): = 2.28–3.31 (m, 2H), 3.32 (s,
hexafluorophosphate
[HOPrT-
1H), 8.98 (m, 2H). 13C (50 MHz, acetone-d6):
d = 30.4, 60.0,
a
61.4, 121.0 (q, JCF = 374 Hz), 128.7, 129.0, 131.4, 145.5,
146.5, 165.8. HRMS(FAB): [C+] (C11H14NO2). Calcd:
192.1025, found: 192.1026.
d
9H), 3.06–3.15 (m, 2H), 4.52 (t, 2H, J = 6.0 Hz), 5.80 (dd, 1H,
J1 = 1.9 Hz, J2 = 10.2 Hz), 6.05 (dd, 1H, J1 = 17.1 Hz,
J2 = 10.2 Hz), 6.15 (dd, 1H, J1 = 1.9 Hz, J2 = 17.2 Hz). 13C
4.8.10. [AcrPrMIm][NTf2] 6a1 (3-acryolyloxypropyl)
methylimidazolium bistrifluoromethanesulfonamide
Following general procedure I using (3-hydropropyl)
(50 MHz, acetone-d6): d = 22.4, 52.7 (t, J = 3.9 Hz), 61.0, 63.8
(t, J = 3.2 Hz), 128.1, 131.2, 165.7. HRMS(FAB): [2C+, PF6]
(C18H36N2O4PF6). Calcd: 489.2317, found: 489.2319.
methylimidazolium
bistrifluoromethanesulfonamide

F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
677
[HOPrMIm][NTf2] and acryloyl chloride, [AcrPrMIm][NTf2]
was obtained in 85% yield as a pale yellow oil. 1H NMR
(200 MHz, acetone-d6):
3.42–3.55 (m, 2H), 4.45 (t, 2H, J = 6.1 Hz), 7.80 (d, 2H,
J = 8.7 Hz), 7.95 (d, 2H, J1 = 8.7 Hz). 13C (50 MHz, acetone-
d
= 1.90–2.05(m, 4H), 3.20 (s, 9H),
(200 MHz, acetone-d6):
d = 2.30–2.50 (m, 2H), 4.15 (s, 3H),
4.28 (t, 2H, J = 6.0 Hz), 4.63 (t, 2H, J = 6.9 Hz), 5.95 (dd, 1H,
J1 = 1.9 Hz, J2 = 10.7 Hz), 6.18 (dd, 1H, J1 = 17.2 Hz,
J2 = 10.7 Hz), 6.40 (dd, 1H, J1 = 1.9 Hz, J2 = 17.2 Hz), 7.80
(t, 1H, J = 1.7 Hz), 7.95 (t, 1H, J = 1.7 Hz), 9.2 (s, 1H). 13C
d6): d = 19.9, 25.5, 53.4 (t, JC-N = 4.1 Hz), 65.1, 66.4, 101.6,
131.2, 131.4, 138.4, 166.8. HRMS(FAB): (2C+, IÀ)
(C14H21NO2I2) 851.1.
(50 MHz, acetone-d6):
d
= 29.3, 36.2, 47.4, 61.4, 121.0 (q,
4.8.15. [IBzBuTMA][PF6] 10d2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium hexafluorophosphate
JCF = 374 Hz), 123.0, 124.3, 128.4, 131.3, 136.9, 166.1.
HRMS(FAB): [C+] (C10H15N2O2). Calcd: 195.1134, found:
192.1132.
Following procedure II using 10f2, [IBzBuTMA][PF6]
was obtained as a white solid in 96% yield. m.p. 204–
206 8C. 1H NMR (200 MHz, acetone-d6):
d = 2.05–2.20 (m,
4.8.11. 4-Dimethylaminobutyl 4-iodobenzoate 92
2H), 2.28–2.47 (m, 2H), 3.6 (s, 9H), 3.80–3.97 (m, 2H), 4.6
To a solution of 4-hydroxybutyldimethylamine (2.8 g,
23.9 mmol) and K2CO3 (6.6 g) in 10 mL of CH2Cl2 were
added at 0 8C 4-iodobenzoyl chloride (7.0 g, 26.3 mmol).
The reaction mixture was allowed to warm up to room
temperature. After 3 h at r.t., the mixture was filtered and
concentrated under reduced pressure to afford 7.3 g of a
colorless oil in analytically pure form (88% yield). 1H NMR
(t, 2H, J = 6.3 Hz), 8 (d, 2H, J = 8.6 Hz), 8.15 (d, 2H, J = 8.6 Hz).
13C (50 MHz, acetone-d6):
d
= 21.0, 26.6, 54.1 (t, J = 4.0 Hz),
65.3, 67.4 (t, J = 3.2 Hz), 101.6, 131.2, 132.3, 139.2, 166.7.
À +
HRMS(FAB): (2C+, PF6
)
(C28H42N2O4F6I2P). Calcd:
869.0876, found: 869.0879.
4.8.16. [IBzBuTMA][NTf2] 10a2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium bistrifluoromethylsulfonamide
Following procedure III using 10f2, [IBzBuTMA][NTf2]
was obtained as a white solid in 90% yield. m.p. 48–50 8C.
(200 MHz, CDCl3):
(t, 2H, J = 5.3 Hz), 4.35 (t, 2H, J = 6.0 Hz), 7.70–7.85 (m, 4H).
13C (50 MHz, CDCl3):
= 20.2, 24.9, 43.5, 57.3, 63.5, 99.0,
d = 1.78–1.90 (m, 4H), 2.50(s, 6H), 2.65
d
128.4, 129.4, 136.2, 164.3.
1H NMR (200 MHz, acetone-d6):
d = 1.82–2.00 (m, 2H),
2.10–2.22 (m, 2H), 3.38 (s, 9H), 3.60–3.72 (m, 2H), 4.40 (t,
4.8.12. [IBzBuTMA][OTf] 10h2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium trifluoromethanesulfonate
To a solution of 92 (4.0 g, 11 mmol) in acetonitrile
(10 mL) was added at 0 8C methyltriflate (1.1 mL,
13.5 mmol). After 15 min at 0 8C, the white solid is filtered
and washed with 3 Â 10 mL of Et2O to afford 4.83 g of a
white solid (96% yield). m.p. 176–178 8C. 1H NMR
2H, J = 6.2 Hz), 7.80 (d, 2H, J = 8.5 Hz), 7.95 (d, 2H,
J = 8.5 Hz). 13C (50 MHz, acetone-d6):
d = 26.7, 29.1, 54.1
(t, JC-N = 4.1 Hz), 65.3, 67.4, 101.6, 121.2 (q, JC-F = 321 Hz),
À +
131.2, 132.3, 139.2, 166.7. HRMS(FAB): (2C+, NTf2
)
(C30H42N3O8F6I2S2). Calcd: 1004.0407, found: 1004.0427.
4.8.17. [IBzBuTMA][Cl] 10g2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium chloride
(200 MHz, CD3CN):
d = 1.80–2.10 (m, 4H), 3.06 (s, 9H),
3.35–3.45 (m, 2H), 4.40 (t, 2H, J = 6.1 Hz), 7.85 (d, 2H,
J = 8.6 Hz), 8 (d, 2H, J1 = 8.6 Hz). 13C (50 MHz, CD3CN):
A solution of [HOBuTMA][Cl], DCC (1.5 eq), 4-iodo-
benzoic acid (1.5 eq) and DMAP (0.2 eq) in acetonitrile
(0.1 M) was allowed to react 4 h at room temperature. After
concentration under reduced pressure, 4-iodobenzoic acid
crushed out upon water addition (10 mL). After filtration
and concentration under vacuum, product was recrystal-
lized in acetone, and used directly in anion metathesis
reactions without further purification.
d
= 19.2, 24.7, 52.5 (t, J = 4.0 Hz), 63.7, 65.6 (t, J = 3.2 Hz),
99.9, 121.3 (q, JC-F = 321 Hz), 129.6, 130.6, 137.6, 165.4.
LRMS(FAB): (2C+, OTfÀ)+ (C29H42N2O7F3I2S) 873.1.
4.8.13. [IBzBuTMA][MeSO4] 10f2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium trifluoromethanesulfate
To a solution of 92 (4.0 g, 11 mmol) in acetonitrile
(10 mL) was added at 0 8C dimethylsulfate (1.24 mL,
13.2 mmol). After 15 min at 0 8C, the white solid was
filtered and washed with 3 Â 10 mL of Et2O to afford 4.99 g
of a white solid (96% yield). m.p. 190–192 8C. 1H NMR
4.8.18. [IBzBuTMA][BF4] 10c2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium tetrafluoroborate
Following procedure IV using 10g2, [IBzBuTMA][BF4]
was obtained as a white solid in 86% yield. m.p. 184–
186 8C. 1H NMR (200 MHz, acetone-d6):
d = 1.90–2.00 (m,
(200 MHz, MeOD):
d
= 1.80–2.10 (m, 4H), 3.20 (s, 9H),
3.38–3.50 (m, 2H), 3.70 (s, 3H), 4.40 (t, 2H, J = 6.0 Hz), 7.78
(dd, 2H, J1 = 2.0 Hz, J2 = 6.8 Hz), 7.90 (dd, 2H, J1 = 2.0 Hz,
2H), 2.15–2.28 (m, 2H), 3.40 (s, 9H), 3.65–3.80 (m, 2H),
4.42(t, 2H, J = 6.3 Hz), 7.85 (d, 2H, J = 8.6 Hz), 8.15 (d, 2H,
J2 = 6.8 Hz). 13C (50 MHz, MeOD):
d
= 21.3, 27.0, 54.3 (t,
J = 8.6 Hz). 13C (50 MHz, acetone-d6):
d
= 21.0, 26.6, 54.0 (t,
J = 3.9 Hz), 56.0, 66.1, 67.8, 102.4, 131.1, 132.5, 139.7,
168.5. HRMS(FAB): (C+) (C14H21NO2I). Calcd: 362.0617,
found: 362.0618.
J = 4.0 Hz), 65.3, 67.4, 101.5, 131.2, 132.3, 139.2, 166.7.
À +
HRMS(FAB): (2C+, BF4
)
(C28H42N2O4F4I2B). Calcd:
811.1263, found: 811.1259.
4.8.14. [IBzBuTMA][I] 10f2 {4-(4-iodobenzoyloxy)
butyl}trimethylammonium iodide
4.8.19. [IBzPrTMA][Cl] 10g1 {3-(4-iodobenzoyloxy)
propyl}trimethylammonium chloride
To a solution of 92 (4.0 g, 11 mmol) in acetonitrile
(10 mL) was added at 0 8C iodomethane (820 mL mL,
13.2 mmol). After 15 min at 0 8C, the white solid was
filtered and washed with 3 Â 10 mL of Et2O to afford 5.32 g
of a white solid (99% yield). m.p. 248–250 8C. 1H NMR
A solution of [HOPrTMA][Cl], DCC (1.5 eq), 4-iodoben-
zoic acid (1.5 eq) and DMAP (0.2 eq) in acetonitrile (0.1 M)
was allowed to react 4 h at room temperature. After
concentration under reduced pressure, 4-iodobenzoic acid
crushed out upon water addition (10 mL). After filtration

678
F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
and concentration under vacuum, product was recrystal-
lized in acetone, and used directly in anion metathesis
reactions without further purification. (95% yield) m.p.
and concentration under vacuum, product was recrystal-
lized in acetone, and used directly in anion metathesis
reactions without further purification.
218–220 8C. 1H NMR (200 MHz, D2O):
d = 2.12–2.35 (m,
2H), 3.12 (s, 9H), 3.38–3.52 (m, 2H), 4.32 (t, 2H, J = 5.9 Hz),
7.65 (dd, 2H, J1 = 1.8 Hz, J2 = 6.6 Hz), 7.83 (dd, 2H,
4.8.25. [IBzHexTMA][BF4] 10c4 {6-(4-iodobenzoyloxy)
hexyl}trimethylammonium tetrafluoroborate
J1 = 1.8 Hz, J2 = 6.7 Hz). 13C (50 MHz, D2O):
d
= 22.6, 53.4
Following procedure IV using 10g4, [IBzHexTMA][BF4]
was obtained as a white solid in 87% yield. m.p. 170–
172 8C. 1H NMR (300 MHz, CD3CN):
d = 1.30–1.62 (m, 4H),
(t, JC-N = 3.9 Hz), 62.8, 64.2, 102.0, 128.8, 131.2, 138.2,
167.8. LRMS(APCI): (C+) (C13H19INO2) 348.3.
1.70–2.02 (m, 4H), 3.30 (s, 9H), 3.45–3.60 (m, 2H), 4.30 (t,
4.8.20. [IBzPrTMA][NTf2] 10a1 {3-(4-iodobenzoyloxy)
propyl}trimethylammonium bistrilfuoromethylsulfonamide
Following procedure III using 10g1, [IBzBuTMA][NTf2]
was obtained as a white solid in 95% yield. m.p. 48–50 8C.
2H, J = 6.5 Hz), 7.80 (dd, 2H, J1 = 1.7 Hz, J2 = 6.7 Hz), 7.90 (dd,
2H, J1 = 1.7 Hz, J2 = 6.7 Hz). 13C (75 MHz, CD3CN):
d = 23.4,
26.2, 26.5, 53.5 (t, J = 3.8 Hz), 65.6, 67.3, 101.0, 128.6, 131.0,
131.8, 138.8, 166.4. LRMS(APCI): (C+) (C16H25INO2) 390.0.
1H NMR (200 MHz, acetone-d6):
d = 2.40–2.60 (m, 2H), 3.47
(s, 9H), 3.80–4.00 (m, 2H), 4.53 (t, 2H, J = 5.9 Hz), 7.83 (d,
2H, J = 8.3 Hz), 7.97 (d, 2H, J = 8.3 Hz). 13C (50 MHz,
4.8.26. [IBzEtMIm][Br] 13b0 {3-(4-iodobenzoyloxy)ethyl}
methylimidazolium bromide
acetone-d6):
d
= 23.1, 53.4 (t, J = 3.8 Hz), 62.2, 64.5, 100.9,
A solution of [HOEtMIm][Br], DCC (1.5 eq), 4-iodoben-
zoic acid (1.5 eq) and DMAP (0.2 eq) in acetonitrile (0.1 M)
was allowed to react 4 h at room temperature. After
concentration under reduced pressure, 4-iodobenzoic acid
crushed out upon water addition (10 mL). After filtration
and concentration under vacuum, product was recrystal-
lized in acetone, and used directly in anion metathesis
reactions without further purification. (92% yield).
120.5 (q, JCF = 321 Hz), 130.0, 131.5, 138.3, 165.7.
LRMS(APCI): (C+) (C13H19INO2) 348.3.
4.8.21. [IBzPrTMA][BF4] 10c1 {3-(4-iodobenzoyloxy)
propyl}trimethylammonium tetrafluoroborate
Following procedure IV using 10g1, [IBzBuTMA][BF4]
was obtained as a white solid in 83% yield. m.p. 190–
192 8C. 1H NMR (200 MHz, acetone-d6):
d = 2.38–2.63 (m,
2H), 3.45(s, 9H), 3.75–3.93 (m, 2H), 4.52 (t, 2H, J = 5.9 Hz),
7.85 (dd, 2H, J1 = 1.9 Hz, J2 = 6.6 Hz), 7.98 (dd, 2H,
4.8.27. [IBzEtMIm][BF4] 13c0 {3-(4-iodobenzoyloxy)ethyl}
methylimidazolium tetrafluoroborate
J1 = 1.9 Hz, J2 = 6.7 Hz). 13C (50 MHz, acetone-d6):
d
= 23.0,
Following procedure IV using 10b0, [IBzEtMIm][BF4]
was obtained as a white solid in 90% yield. m.p. 146–
148 8C. 1H NMR (300 MHz, acetone-d6):
d = 4.10 (s, 3H),
53.2 (t, J = 4.0 Hz), 62.3, 64.2, 100.8, 130.0, 131.6, 138.3,
165.8. LRMS(APCI): (C+) (C13H19INO2) 348.3.
4.73–4.82 (m, 2H), 4.85–4.92 (m, 2H), 7.75–7.85 (m, 3H),
4.8.22. [IBzEtTMA][Cl] 10g0 {2-(4-iodobenzoyloxy)ethyl}
trimethylammonium chloride
7.92–8.00 (m, 3H), 9.27 (s, 1H). 13C (75 MHz, acetone-d6):
d
= 36.7, 49.5, 64.2, 101.6, 124.0, 124.9, 130.0, 132.1, 138.2,
A solution of [HOEtTMA][Cl], DCC (1.5 eq), 4-iodoben-
zoic acid (1.5 eq) and DMAP (0.2 eq) in acetonitrile (0.1 M)
was allowed to react 4 h at room temperature. After
concentration under reduced pressure, 4-iodobenzoic acid
crushed out upon water addition (10 mL). After filtration
and concentration under vacuum, product was recrystal-
lized in acetone, and used directly in anion metathesis
reactions without further purification (93% yield).
138.9, 166.0. LRMS(APCI): (C+) (C13H14IN2O2) 357.0.
4.8.28. [CinPrTMA][NTf2] Ph-14a1 {3-(3-phenylprop-2-
enoylox)propyl}trimethylammonium
bistrifluoromethanesulfonamide
Following general procedure V using 3a1 and iodoben-
zene in DMF, [CinPrTMA][NTf2] was obtained in 86% yield
as a purple solid. m.p. 172–174 8C 1H NMR (300 MHz,
CD3CN):
d = 2.18–2.35 (m, 2H), 3.15 (s, 9H), 3.43–3.58 (m,
4.8.23. [IBzEtTMA][BF4] 10c0 {2-(4-iodobenzoyloxy)ethyl}
trimethylammonium tetrafluoroborate
2H), 4.34 (t, 2H, J = 5.9 Hz), 6.55 (d, 1H, J = 16.1 Hz), 7.41–
7.53 (m, 3H), 7.65–7.88 (m, 3H). 13C (75 MHz, CD3CN):
Following procedure IV using 10g0, [IBzEtTMA][BF4]
was obtained as a white solid in 90% yield. m.p. 200–
d = 22.9, 53.6, 61.3, 64.2, 118.1, 128.7, 129.4, 131.0, 134.7,
145.4, 167.0. LRMS(APCI): [C+] (C15H22NO2) 248.2.
202 8C. 1H NMR (300 MHz, CD3CN):
d = 3.18 (s, 9H), 3.68–
3.80 (m, 2H), 4.50–4.73 (m, 2H), 7.78 (dd, 2H, J1 = 1.9 Hz,
J2 = 6.7 Hz), 7.90 (dd, 2H, J1 = 1.8 Hz, J2 = 6.6 Hz). 13C
4.8.29. [tBuOCOCHCHBzPrTMA][NTf2] 15c1 {3-(2-tert-
butoxycarbonylvinyl)benzoyloxypropyl}trimethylammonium
bistrifluoromethanesulfonamide
(75 MHz, CD3CN):
d = 53.4 (t, J = 3.8 Hz), 58.3, 64.4 (t,
J = 3.8 Hz), 100.6, 128.6, 130.7, 137.8, 164.7. LRMS(APCI):
Following general procedure VI using 10c1 and
tertbutylacrylate in DMF, [tBuOCOCHCHBzPrTMA][NTf2]
was obtained in 86% yield as a brown solid. m.p. 170–
(C+) (C12H17INO2) 334.0.
4.8.24. [IBzHexTMA][Cl] 10g4 {6-(4-iodobenzoyloxy)hexyl}
trimethylammonium chloride
172 8C 1H NMR (300 MHz, CD3CN):
d = 1.53 (s, 9H), 2.18–
2.35 (m, 2H), 3.15 (s, 9H), 3.43–3.58 (m, 2H), 4.44 (t, 2H,
A solution of [HOEtTMA][Cl], DCC (1.5 eq), 4-iodoben-
zoic acid (1.5 eq) and DMAP (0.2 eq) in acetonitrile (0.1 M)
was allowed to react 4 h at room temperature. After
concentration under reduced pressure, 4-iodobenzoic acid
crushed out upon water addition (10 mL). After filtration
J = 5.8 Hz), 6.55 (d, 1H, J = 16.1 Hz), 7.58–7.78 (m, 3H), 8.09
(d, 2H, J = 8.4 Hz). 13C (75 MHz, CD3CN):
d = 22.0, 26.9, 52.6
(t, J = 4.0 Hz), 61.4, 63.4 (t, J = 3.3 Hz), 80.6, 122.3, 127.8,
129.6, 130.4, 138.8, 141.7, 165.6, 165.6. LRMS(APCI): [C+]
(C20H30NO4) 348.3.

F. Hassine et al. / C. R. Chimie 14 (2011) 671–679
679
[22] P. Lozano, T. Diego, M. Larnicol, M. Vaultier, J.L. Iborra, Biotech. Lett. 28
4.8.30. Methyl cinamate [103-26-4]
(2006) 1559.
A 1 M HCl solution of supported cinnamate (0.1 M) was
heated to reflux under argon atmosphere. After 3 h,
methanol was removed under reduced pressure. The
product was extracted from the remaining oil by adding
five times 4 mL/mmol of Et2O. After concentration of the
ether fraction under reduced pressure, methyl cinnamate
was obtained in 97% yield with > 99% purity (GC/MS).
[23] P. Lozano, T. de Diego, D. Carrie, M. Vaultier, J.L. Iborra, Chem. Commun.
(2002) 692.
[24] P. Lozano, T. de Diego, S. Gmouh, M. Vaultier, J.L. Iborra, Biotech. Prog.
20 (2004) 661.
[25] P. Lozano, T. De Diego, J.P. Guegan, M. Vaultier, J.L. Iborra, Biotech.
Bioeng. 75 (2001) 563.
[26] C.E. Song, Chem. Commun. (2004) 1033.
[27] N. Jain, A. Kumar, S. Chauhan, S.M.S. Chauhan, Tetrahedron 61 (2005)
1015.
[28] P. Wasserscheid, Transition metals for organic synthesis, 2nd ed., 2
(2004) 559.
References
`
[29] V. Calo, A. Nacci, A. Monopoli, Eur. J. Org. Chem. 2006 (2006) 3791–
3802.
[1] K.C. Nicolaou, R. Hanko, W. Hartwig, Wiley-VCH, Weinheim, 2002.
[2] H. Qian, C. Lu, Z. Ye, J. Huagong 23 (2006) 362.
[3] I.T. Horvath, J. Rabai, Science 266 (1994) 72.
[4] D.P. Curran, H. Nakamura, I. Ryu, H. Matsubara, University of Pitts-
burgh, USA, US2003125590, 2003, pp. 36, Cont. -in-part of US Ser No.
877,944.
[30] P. Wasserscheid, T. Welton, Ionic liquids in Synthesis, 2nd ed., Wiley-
VCH, Verlag, 2008.
[31] D. Kaufmann, M. Nouroozian, H. Henze, Synlett (1996) 1091.
[32] A.J. Carmichael, M.J. Earle, J.D. Holbrey, P.B. McCormac, K.R. Seddon,
Org. Lett. 1 (1999) 997.
[33] W.A. Herrmann, V.P.W. Bohm, J. Organomet. Chem. 572 (1999)
141.
[34] F. Alonso, I.P. Beletskaya, M. Yus, Tetrahedron 61 (2005) 11771.
[35] V. Polshettiwar, Res. J. Chem. Environ. 10 (2006) 91.
[36] L. Zhou, L. Wang, Synthesis (2006) 2653.
[37] B. Yoon, C.H. Yen, S. Mekki, S. Wherland, C.M. Wai, Ind. Eng. Chem. Res.
45 (2006) 4433.
[38] S. Li, Y. Lin, H. Xie, S. Zhang, J. Xu, Org. Lett. 8 (2006) 391.
[39] H. Hagiwara, Y. Sugawara, K. Isobe, T. Hoshi, T. Suzuki, Org. Lett. 8
(2006) 1749.
[5] S. Roller, C. Siegers, R. Haag, Tetrahedron 60 (2004) 8711.
[6] D.E. Bergbreiter, Chem. Rev. 102 (2002) 3345.
[7] D.J. Gravert, K.D. Janda, Chem. Rev. 97 (1997) 489.
[8] P.H. Toy, K.D. Janda, Acc. Chem. Res. 33 (2000) 546.
[9] H. Hellermann, H.W. Lucas, J. Maul, V.N.R. Pillai, M. Mutter, Makromol.
Chem. 184 (1983) 2603.
[10] S.P. Douglas, D.M. Whitfield, J.J. Krepinsky, J. Am. Chem. Soc. 113 (1991)
5095.
[11] H. Koester, Tetrahedron Lett. (1972) 1535.
[12] T. Welton, Chem. Rev. 99 (1999) 2071.
[40] R. Wang, B. Twamley, J.M. Shreeve, J. Org. Chem. 71 (2006) 426.
[41] R. Wang, M.M. Piekarski, J.M. Shreeve, Org. Biomol. Chem. 4 (2006)
1878.
[13] M. Pucheault, M. Vaultier, Top. Curr. Chem. 290 (2009) 86.
[14] M. Vaultier, S. Gmouh, F. Hassine, in: CNRS, U. Rennes
WO2005005345, 2003, pp. 190.
1 (Eds.),
[42] C. Brochwitz, A. Feldhoff, U. Kunz, M. Vaultier, A. Kirschning, Lett. Org.
Chem. 3 (2006) 442.
[15] M. Vaultier, S. Gmouh, in: CNRS, U. Rennes 1 (Eds.), WO2004029004,
2002, pp. 129.
[43] J. Mo, L. Xu, J. Xiao, J. Am. Chem. Soc. 127 (2005) 751.
[44] L. Xu, W. Chen, J. Xiao, Organometallics 19 (2000) 1123.
[45] T. Jeffery, Tetrahedron Lett. 26 (1985) 2667.
[46] M.T. Reetz, E. Westermann, Angew. Chem. Int. Ed. 39 (2000) 165.
[47] V.P.W. Bo¨hm, W.A. Herrmann, Chem. Eur. J. 6 (2000) 1017.
[48] L. Xu, W. Chen, J. Xiao. Organometallics 19 (2000) 1123.
[49] For the use of homeopathic palladium see: A.H.M. de Vries,
J.M.C.A. Mulders, J.H.M. Mommers, H.J.W. Henderickx, J.G. de Vries,
Org. Lett. 5 (2003) 3285.
[16] M. Vaultier, A. Kirschning, V. Singh, Ionic Liq. Synth. (2nd Ed.) 2 (2008)
488.
[17] M. Vaultier, C. Roche, S. Gmouh, A. Commercon, in: F. Aventis Pharma
SA, CNRS (Eds.), WO2008003836, 2005, pp. 67.
[18] J. Verron, J.M. Joerger, M. Pucheault, M. Vaultier, Tetrahedron Lett. 48
(2007) 4055.
[19] A. Ouach, M. Pucheault, M. Vaultier, Heterocycles 73 (2007) 461.
[20] A. Ouach, S. Gmouh, M. Pucheault, M. Vaultier, Tetrahedron 64 (2008)
1962.
[50] W.L.F. Armarego, C.L.L. Chai. (Eds.), Purification of laboratory chemicals,
5th ed., 2003.
[21] J.C. Legeay, J.Y. Goujon, J.J. VandenEynde, L. Toupet, J.P. Bazureau,
J. Comb. Chem. 8 (2006) 829.