Journal of Molecular Catalysis A: Chemical 381 (2014) 120125

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Journal of Molecular Catalysis A: Chemical

journal homepage: www.elsevier.com/locate/molcata

Carbonylation of quaternary ammonium salts to tertiary amides using

NaCo(CO)4 catalyst
Yizhu Lei a , Rui Zhang a , Qing Wu a , Hui Mei a , Bo Xiao b , Guangxing Li a,
a
School of Chemistry and Chemical Engineering, Hubei Key Laboratory of Material Chemistry and Service Failure, Huazhong University of Science and
Technology, Luoyu Road 1037, Wuhan, Hubei 430074, PR China
b
College of Environment Science and Engineering, Huazhong University of Science and Technology, Luoyu Road 1037, Wuhan, Hubei 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: We reported here the catalytic carbonylation of quaternary ammonium salts under anhydrous condi-
Received 26 June 2013 tion. Quaternary ammonium salts, a kind of versatile reagents that were widely used in organometallic
Received in revised form 12 October 2013 chemistry, can be carbonylated to tertiary amides by an in situ prepared NaCo(CO)4 catalyst. It was found
Accepted 20 October 2013
that the counterions (Cl , Br , I , OTf ) in the quaternary ammonium salts played a signicant role in
Available online 27 October 2013
the reaction and tetramethylammonium iodide could give high yield (96%) of N,N-dimethylacetamide
(DMAc) with only 0.5 mol% cobalt catalyst. Under optimum conditions, several other quaternary ammo-
Keywords:
nium iodides were also carbonylated to corresponding tertiary amides in moderate to excellent yields.
Carbonylation
Quaternary ammonium salt
Obviously, these results also give us a special apprehension that Me4 NI and other quaternary ammonium
Tertiary amide salts could be possibly carbonylated to tertiary amides in the carbonylation reaction where they are used
NaCo(CO)4 catalyst as promoters or solvents in most cases. Considering the high activity and moderate to excellent selectiv-
ity, this process could be a potential method for the synthesis of certain tertiary amides. Moreover, the
cleaving mechanism of C N bonds and the possible catalytic intermediates were discussed in detail.
2013 Elsevier B.V. All rights reserved.

1. Introduction the main products employing benzyltriethylammonium or allyltri-

Quaternary ammonium salt, a versatile reagent, is widely used
as phase transfer catalyst, catalyst promoter or ionic liquid sol-
vent in organometallic chemistry and homogeneous carbonylation
reactions [14]. Generally, quaternary ammonium salts are con-
sidered to be very stable for their high decomposition temperature
[5,6]. The reactivity of quaternary ammonium salt is usually easy
to ignore in transition metal catalyzed reaction. Since Wenkert
et al. documented the rst cross coupling of aryltrimethylammo-
nium iodides with aryl and alkyl Grignard reagents in 1988 [7],
transition-metal-catalyzed cross-coupling of quaternary ammo-
nium salts with various nucleophile coupling partners is becoming
an attractive topic [810]. And now, transformations of amines
to their salts are also becoming one of the main methods for the
functionalization of unreactive C N bonds [1113].
Although it was also known in the 1980s [14], the potential for
carbonylation of quaternary ammonium salts has not received a
great deal of attention, and in fact, only a few results have been
reported to date [14,15]. These reactions were usually involved
a C6 H6 /aqueous NaOH biphasic system and carboxylic acids as
Corresponding author. Tel.: +86 27 87543632; fax: +86 27 87543632.
E-mail address: ligxabc@163.com (G. Li).
ethylammonium halides as substrates. Recently, we found that the
tetramethylammonium iodide was in equilibrium with MeI and the
Me3 N at 220 C [16,17]. It suggests the high possibility that Me4 NI
could be carbonylated to DMAc at 220 C. Moreover, quaternary
ammonium salts are widely used as phase-transfer catalysts, cata-
lyst promoters and ionic liquid solvents in many catalytic reactions,
especially in homogeneous carbonylation reactions [14]. There-
fore, it is very valuable to investigate the stability and reactivity of
different quaternary ammonium salts under anhydrous carbonyla-
tion reaction conditions.
From the other points of view, amide bond formation, one of the
most important reactions in organic chemistry, is often overlooked
as a contemporary topic due to its widespread occurrence of amide
in chemistry and biology [1821]. As an important class of amide
compounds, tertiary amides were also frequently used as precur-
sors to unsymmetrical tertiary amines [22,23]. However, traditional
synthesis method of tertiary amides via coupling of carboxylic
acid derivatives and secondary amines is suffering from tedious
processes and poor atom economy. Therefore, there is continuing
interest in the development of new and improved methodolo-
gies for their synthesis [2437]. As an alternative method for the
synthesis of tertiary amides, efforts have also been made to syn-
thesize tertiary amides by direct carbonylation of tertiary amines
[16,17,38,39]. As the more reactive reagent, however, quaternary

1381-1169/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molcata.2013.10.014
 Y. Lei et al. / Journal of Molecular Catalysis A: Chemical 381 (2014) 120125
Scheme 1. Cobalt catalyzed carbonylation of quaternary ammonium salts.
ammonium salts have not yet been employed as the substrates for
the synthesis of tertiary amides.
Based on our previous work on transition metal-catalyzed
carbonylation reactions and continuing focus on the application
of quaternary ammonium salts in homogeneous carbonylation
reactions [16,17,40,41]. Herein, we established the carbonyla-
tion of quaternary ammonium salts under anhydrous condition
(Scheme 1). Due to its high catalytic activity and moderate to excel-
lent selectivity, this process can be a promising method for the
synthesis of certain tertiary amides. Moreover, the cleaving mech-
anism of C N bonds was discussed and a plausible mechanism was
also proposed.
2. Experimental
2.1. Reagents
All reagents were analytical grade and used without
further purication. N-methyl pyrrolidone (NMP), N,N-
dimethylformamide (DMF) and toluene were analytical grade
and dried before use by normal procedures. CO with a purity of
99.99% was purchased from the local manufacturer. NaCo(CO)4
was prepared as our previous publication [16].
2.2. Catalytic experiments
The catalytic reactions were carried out in a 250 mL stainless
steel autoclave. In a typical experiment, CoCl2 , Zn, Na2 SO3 , quater-
nary ammonium salt and NMP were charged into the autoclave.
After purging four times with CO, the autoclave was pressurized
with CO to 3.0 MPa, heated and kept at 200 C for 7 h. During the
reaction, CO was added to maintain a total pressure of 4.0 MPa.
After the reaction, autoclave was cooled by ice water and slowly
depressurized to atmospheric pressure.
The liquid mixture taken from the autoclave after the reac-
tion was analyzed qualitatively by GCMS. The analyses were
performed in an Agilent 6890/5973 GCMS apparatus equipped
with a split/splitless injection system and a ame ionization
detector (FID). The capillary column was an Agilent HP-5MS,
30 m 0.25 mm 0.25 m. He was used as the carrier gas
(1.0 mL/min). The quantitative analysis of the reaction mixture was
carried out in an Agilent GC 1790 apparatus equipped with a HP-
5 (30 m 0.32 mm 0.25 m) capillary column, a ame ionization
detector (FID) and using n-butanol as an internal standard.
2.3. Quantitative analysis of quaternary ammonium salts
Quantitative analysis of quaternary ammonium salt was made
by a method described in literature with some modication [42].
After the reaction, the reaction mixture was ltrated to remove
solid residues. The ltrate obtained was vacuum distilled to remove
the liquid substances. Then the residual solid was dissolved in
water, and after that, an excess amount of aqueous sodium
tetraphenylborate solution was added dropwise into the solution
and the white precipitate was formed immediately. To insure the
fully precipitation of quaternary ammonium tetraphenylborate,
121
appropriate amount of NaCl solution was added, and then the pre-
cipitate was ltrated, dried and weighed.
2.4. Amine exchange reaction
Me4 NI (10 mmol), N,N-diethylaniline (10 mmol) and NMP
(50 mL) were charged into the autoclave. After purging four times
with N2 , the autoclave was heated and then kept at the reaction
temperature for 7 h. After the reaction, autoclave was cooled by ice
water and analyzed by GC and GCMS.
3. Results
3.1. Effect of counterion and solvent
Initially, the carbonylation of tetramethylammonium salt bear-
ing different anions (I , Br , Cl and OTf ) was chosen as a model
reaction. [Co(CO)4 ] , which could be prepared under mild condi-
tions, was used as a catalyst. When the as-prepared NaCo(CO)4
(5 mol%) was used at 3.0 MPa CO and 200 C, 13.3% yield of DMAc
was observed in the carbonylation of tetramethylammonium chlo-
ride (Table 1, entry 1). Encouraged by this initial result, we tried to
investigate the activity of different tetramethylammonium salts.
Fortunately, tetramethylammonium iodide gave 98.2% yield of
DMAc with MeI as the only byproduct (Table 1, entry 4). Mean-
while, the bromide and triate gave moderate yields of DMAc
(Table 1, entries 2 and 3). These results suggested that the anion
had a great effect on the activity of tetramethylammonium salts,
and their reactivity increased in the order Cl < OTf < Br < I. Moreover,
as tetramethylammonium iodide is conventionally synthesized by
the quaternization reaction of methyl iodide and trimethylamine.
After the catalytic carbonylation of tetramethylammonium iodide,
the byproduct (MeI) could be easily recovered by a simple process
(see supplementary content) and reused again as the raw mate-
rial for the synthesis of tetramethylammonium iodide. Since a high
recovery of methyl iodide could be achieved, then the poor atom
economy of this process is mitigated and the raw material costs
could be reduced.
It is well-known that solvent is very important in a liquid phase
catalytic reaction, even more so in a two-liquid phase reaction
[4,43]. Therefore, the solvent effect on the reaction was tested.
Similarly, the reaction in DMF solvent gave 93.0% yield of DMAc
(Table 1, entry 5). In contrast, only 64.5% yield of the desired prod-
uct was achieved in toluene (Table 1, entry 6). To achieve the easy
separation of the catalyst and product, the reaction was also tried
in a biphasic solvent system. When the reaction was carried out
in a toluene-water mixture, very low activity and selectivity were
obtained. Increasing the amount of water in the reaction led to
lower catalytic activity and selectivity of DMAc. Meanwhile, the
yield of acetic acid rapidly increased (Table 1, entries 7 and 8).
3.2. Effect of catalyst and catalyst dosage
Having established the better reactivity of iodide over other
salts, then we explored alternative catalyst to simplify the prepa-
ration procedure of the catalyst and to lower the catalyst dosage.
First, an attempt had been made to use CoCl2 as a catalyst directly,
while only a trace amount of product was observed (Table 2, entry
1). Then, we tried to use CoCl2 as a catalyst precursor for in situ
preparation of NaCo(CO)4 during the catalytic reaction. Notably,
when 5 mol% of CoCl2 and proper amount of reducing agents were
directly added to the reaction, quantitative conversion along with
selectivity (98.8%) was obtained (Table 2, entry 2). The exceptional
reactivity of the tetramethylammonium iodide suggested that the
catalyst dosage could be lowered further; this was indeed possible
122 Y. Lei et al. / Journal of Molecular Catalysis A: Chemical 381 (2014) 120125

Table 1
Effect of counterion and solvent.a

Entry Solventb Counterion Time (h) Conversion (mol%) Selectivity (mol%) YieldDMAc (mol%)d Acetic acid (mol%)d

1 NMP Cl 14 13.6 97.5 13.3
2 NMP Br 14 65.7 98.1 64.5
3 NMP OTf 14 55.0 97.2 53.5
4c NMP I 7 99.7 98.5 98.2
5 DMF I 7 95.6 97.2 93.0
6 Toluene I 7 65.4 98.7 64.5
7 Toluene/water (9:1) I 7 55.8 63.0 35.2 19.4
8 Toluene/water (1:1) I 7 32.1 12.7 4.1 11.0
a
Reaction conditions: NaCo(CO)4 (0.75 mmol); tetramethylammonium salt (15 mmol); solvent (50 mL); CO (3 MPa); 200 C; stirring speed, 500 rpm.
b
Toluene/water (weight ratio).
c
Yield of MeI 98.0 mol%.
d
Yield = nnx 100% (nx , the molar number of the product; n0 , the molar number of the initially added ammonium salt).
0

Table 2
Effect of catalyst and catalyst dosage.a

Entry Catalyst Substrate:catalyst molar ratio Conversion (mol%) Selectivity (mol%) Yield (mol%) TONb

1 CoCl2 20 6.3 99.0 6.2 1.2

2 CoCl2 /Zn/Na2 SO3 20 99.6 98.8 98.4 19.7
3 CoCl2 /Zn/Na2 SO3 50 99.8 98.7 98.5 49.3
4 CoCl2 /Zn/Na2 SO3 100 99.5 98.7 98.2 98.2
5 CoCl2 /Zn/Na2 SO3 200 97.4 98.9 96.3 192.6
6 CoCl2 /Zn/Na2 SO3 400 83.3 98.7 82.2 328.8
7 NaCo(CO)4 400 84.9 98.5 83.6 334.4
a
Reaction conditions: CoCl2 :Zn:Na2 SO3 = 1:1.33:1 (mole ratio); Me4 NI (15 mmol); NMP (50 mL); CO (3 MPa); 200 C; reaction time, 7 h; stirring speed, 500 rpm.
b
TON (mol converted Me4 NI/mol cat.).

and the reaction proceeded almost equally as fast with 0.5 mol% cat-
alyst (Table 2, entry 5). Next experiments revealed that this in situ
synthesis of NaCo(CO)4 showed almost the same catalytic activity
as the as-prepared NaCo(CO)4 (Table 2, entries 6 and 7). It must be
noted that the catalytic activity of this process is much higher than
those reported for the carbonylation of trimethylamine [16,17].
3.3. Effect of temperature and CO pressure
Quaternary ammonium salts are widely used as phase-transfer
catalysts, catalyst promoters and ionic liquid solvents in catalytic
carbonylation reaction [4]. However, the reactivity of quaternary
ammonium salts in catalytic carbonylation reactions is seldom
documented. Alper and Caubere have reported that benzyltri-
ethylammonium and allyltriethylammonium halides could be
carbonylated to corresponding acids in a C6 H6 /aqueous NaOH
solution [14,15]. Unfortunately, substrates in these reports were
only limited to aryl or benzyl quaternary ammonium halides
and the reactions took place under specic conditions, that is, in
C6 H6 /aqueous NaOH solution. To investigate the reactivity of qua-
ternary ammonium salts in anhydrous organic solvent, the effect of
reaction temperature and CO pressure on the carbonylation in NMP
solvent was examined (in Table 3). It was found that Me4 NI could
react with CO in a very low rate at 140 C (Table 3, entry 2). With
the increase of reaction temperature from 140 C to 180 C, Me4 NI
conversion increased signicantly and a consistent selectivity of
DMAc was preserved (Table 3, entries 24). Further increasing the
temperature to 200 C, much higher yield of DMAc was obtained
(Table 3, entry 5). The inuence of pressure on the carbonylation
of Me4 NI was presented in Table 3 (entries 58). It is obvious that
there is a signicant relationship between the conversion and the
CO pressure. The conversion increased notably from 12.1% to 97.4%
when the pressure varied from 0.5 to 3.0 MPa.
3.4. Carbonylation of quaternary ammonium iodides
The results of carbonylation of several quaternary ammonium
iodides were given in Table 4. Ethyltrimethylammonium iodide
gave excellent conversion with moderate selectivity. Alicyclic
quaternary ammonium salts, such as N,N-dimethylpyrrolidinium
iodide and N,N-dimethylpiperidinium iodide, reacted with CO
to afford the corresponding amides in moderate to excellent
yields (Table 4, entries 2 and 3). N,N-dimethylmorpholinium
iodide, as a representative example of heterocyclic quaternary
ammonium salt, resulted in 72.3% yield of N-acetylmorpholine
(Table 4, entry 4). Aryltrimethylammonium iodide, one of the
most common substrates in cross coupling reaction [7,10], gave
N-methyl-N-phenyl-acetamide in 93.7% yield (Table 4, entry
5). Aryltriethylammonium iodide and benzyltrimethylammonium
iodide gave the corresponding products in 49.7% and 41.7% yield,
respectively (Table 4, entries 6 and 7). These results demonstrated
that the carbonylation of quaternary ammonium salts was a com-
mon phenomenon under these carbonylation reaction conditions.
Obviously, it gives us a special alarm that Me4 NI and other qua-
ternary ammonium salts could be possibly carbonylated to tertiary
amides in the carbonylation reaction where they are used as pro-
moters or solvents in most cases, more or less, which would be
interfere the main carbonylation reaction.
4. Discussion
4.1. C N bond cleavage of quaternary ammonium salts
The cleavage of C N bonds to form useful N-containing ne
chemicals is of signicant interest because such bonds are very
common in organic chemistry [44,45]. However, C N bonds are
generally very strong and usually difcult to cleave. For the func-
tionalization of the unactivated C N bonds, the bonds are usually
activated by conversion to their salts [713]. Therefore, investiga-
tion about the cleaving mechanism of C N bonds in ammonium
salts could be informative for such kinds of reactions. We orig-
inally assumed that C N bonds in quaternary ammonium salts
could be cleaved either by the thermal decomposition or by the
nucleophilic attack of [Co(CO)4 ] on the electropositive nitrogen
atom. However, Me4 NI and other ammonium salts were reported
to be thermally quite stable even at much higher temperature
 Y. Lei et al. / Journal of Molecular Catalysis A: Chemical 381 (2014) 120125 123

Table 3
Effect of temperature and CO pressure.a

Entry T ( C) Pressure (MPa) Conversion (mol%) Selectivity (mol%) YieldDMAc (mol%) TONb

1 120 3
2 140 3 7.2 98.8 7.1 14.2
3 160 3 27.2 98.6 26.8 53.6
4 180 3 91.8 98.9 90.8 181.6
5 200 3 97.4 98.9 96.3 192.6
6 200 2 91.7 98.4 90.2 180.4
7 200 1 56.9 98.1 55.8 111.6
8 200 0.5 12.1 98.5 11.9 23.8
a
Reaction conditions: CoCl2 (0.075 mmol); Zn (0.1 mmol); Na2 SO3 (0.075 mmol); Me4 NI (15 mmol); NMP (50 mL); reaction time, 7 h; stirring speed, 500 rpm.
b
TON (mol converted Me4 NI/mol cat.).

Table 4
Cobalt catalyzed carbonylation of quaternary ammonium iodides.a

Entry Quaternary ammonium salts Products Conversion (mol%) Selectivity (mol%) Yield (mol%)

1 98.1 78.7 77.2

2 99.5 95.4 94.9

3 98.6 83.0 81.8

4 97.4 74.2 72.3

5 97.8 95.8 93.7

6b 88.6 56.1 49.7

7b 92.4 45.2 41.7

a
Reaction conditions: CoCl2 (0.075 mmol); Zn (0.1 mmol); Na2 SO3 (0.075 mmol); quaternary ammonium salt (15 mmol); NMP (50 mL); CO (3 MPa); 200 C; reaction time,
7 h; stirring speed, 500 rpm.
b
Reaction temperature: 180 C, 12 h.

[5,6]. But considering the differences of reaction conditions, the
thermal behavior of Me4 NI in the solution might be quite differ-
ent. Taking this matter into account, an amine exchange reaction
between Me4 NI and N,N-diethylaniline was conducted (Table 5).
The results indicated that Me4 NI could be thermally decomposed
at 200 C and Me4 NI would be in equilibrium with MeI and Me3 N
under the reaction conditions. However, when the exchange reac-
tion was conducted at 150 C, no Me3 N was detected (Table 5, entry
3). These results suggested that Me4 NI did not thermally decom-
pose at 150 C. It is concluded that the cleavage of C N bonds in the
catalytic carbonylation of Me4 NI below 150 C should be attributed
to catalytic transformation of Me4 NI by [Co(CO)4 ] (Table 3,
entry 2).
Table 5
Amine exchange reaction between Me4 NI and N,N-diethylaniline.a
Entry T ( C) Yield of Me3 N (%)b
1 200 27.3
2 180 6.4
3 150 0 the same propionyl group were obtained (Table 6, entry 3). These
a
Reaction conditions: Me4 NI (10 mmol); N,N-diethylaniline (10 mmol); NMP
(50 mL); reaction time, 7 h; stirring speed, 500 rpm.
4.2. The acyl complex intermediates
Based on the results above, we assumed that the intermediates
should be the acylcobalt tetracarbonyl and acyl halide. Just like the
mechanism of cobalt carbonyl catalyzed carbonylation of methanol
to acetic acid [46], acylcobalt tetracarbonyl could be generated
from alkyl iodide and Co(CO)4 , and then acylcobalt tetracarbonyl
reacted with iodide ion to produce acyl halide. The presence of
acetic acid as byproduct (Table 1, entries 7 and 8) could be indi-
rect evidence for the existence of acyl complex intermediate [46].
To gain additional insight into the catalytic intermediates and to
conrm the presence of acyl complex in this reaction, additional
experiments about catalytic carbonylation of quaternary ammo-
nium iodide were carried out in the presence of tertiary amine
(Table 6). If the acylcobalt tetracarbonyl existed, the generated acyl
halide should react with both the added tertiary amine as well as
the one produced, thus resulted in different tertiary amides [47]. As
we expected, when tetramethylammonium iodide was carbony-
lated in the presence of other tertiary amines (Table 6, entries 1
and 2), different tertiary amides bearing the same acetyl group
were obtained. Likewise, when aryltriethylammonium iodide was
mixed with trimethylamine, two kinds of tertiary amides bearing
results in Table 6 give us a positive reply and a further evidence of
the existence of the acyl complex.
124 Y. Lei et al. / Journal of Molecular Catalysis A: Chemical 381 (2014) 120125
Table 6
Cobalt catalyzed carbonylation of quaternary ammonium iodide in the presence of tertiary amine.a
Entry Ammonium salt Tertiary amine
1 Me4 NI (C2 H5 )3 N
2 Me4 NI PhNEt2
3 Me3 N
a
Reaction conditions: CoCl2 (0.075 mmol); Zn (0.1 mmol); Na2 SO3 (0.075 mmol); quaternary ammonium iodide (15 mmol); tertiary amine (15 mmol); NMP (50 mL); CO
(3 MPa); 200 C; reaction time, 3 h; stirring speed, 500 rpm.
b
Yield of A: based on the amount of the added ammonium iodides; Yield of B: based on the amount of the added tertiary amine.
Scheme 2. Proposed mechanism for carbonylation of quaternary ammonium salts.
4.3. Mechanistic considerations
Taking into account of the results published about cobalt-
catalyzed carbonylation and the discussions above [46], herein, we
proposed a reaction mechanism for the formation of tertiary amides
by the carbonylation of quaternary ammonium salts in the presence
of cobalt carbonyl in Scheme 2.
Initially, NaCo(CO)4 was in situ generated under the reac-
tion condition. Next, R1 X and tertiary amine could be formed by
the catalytic and/or thermal cleavage of C N bond in quaternary
ammonium salt. Then, the nucleophilic attack of the [Co(CO)4 ] to
R1 X leads to the species B. Subsequent migratory insertion of a coor-
dinated CO ligand to Co C bond affords species C. One molecule of
CO is coordinated and results in 18e tetracarbonyl intermediate the
species D. Then, species D reacts with counterion to produce R1 COX.
R1 COX is converted along with the generated tertiary amine to give
the nal tertiary amide, at the same time, R1 X is regenerated.
5. Conclusions
In conclusion, the carbonylation of quaternary ammonium salt
was a common phenomenon under carbonylation reaction condi-
tions. It gives us a special apprehension that quaternary ammonium
salts themselves could be possibly carbonylated to tertiary amides
Yield (%)b
A B
(55.3) (20.7)
(59.0) (12.6)
(10.6) (32.1)
in carbonylation reaction where they are used as promoters or
solvents in most cases. Due to the high catalytic activity and recy-
clability of alkyl iodide, this process can be a potential procedure for
the preparation of certain tertiary amides. Moreover, the cleaving
mechanism of C N bonds and the possible catalytic intermediates
were discussed in detail; these could be also informative for other
reactions which involved the cleaving C N bond of ammonium
salts or tertiary amines.
Acknowledgements
This work is partly supported nancially by the 863 Program
of Ministry of Science and Technology of China (NC2010MA0137).
Thankfulness is expressed for the spectroscopic analysis to the
Analytical and Testing Center, Huazhong University of Science and
Technology, Wuhan, China.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.molcata.
2013.10.014.
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