CsF/clinoptilolite: An efficient solid base in SNAr and copper-catalyzed Ullmann reactions

Article abstract of DOI:10.1139/cjc-2015-0300

CsF/clinoptilolite was found to be an efficient solid base catalyst for both S_NAr and Ullmann ether reactions. A general and efficient one-step procedure was developed for the synthesis of biaryl ethers via direct coupling of electron-deficient aryl halides to phenols using CsF/clinoptilolite. The protocol was also applied to electron-rich aryl halides by addition of a catalytic amount of copper oxide nanoparticles. Both S_NAr and Ullmann reactions were rapid and provided good to excellent yields.

Full text of DOI:10.1139/cjc-2015-0300

Page 1 of 30
CsF/Clinoptilolite: an Efficient Solid Base in S Ar
N
and Copper-catalyzed Ullmann Reactions
a,b
b
b
b
Hoda Keipour , Abolfazl Hosseini , Amir Afsari , Razieh Oladee ,
b
a
Mohammad A. Khalilzadeh* and Thierry Ollevier*
a
Département de chimie, Université Laval, 1045 avenue de la Médecine, Québec, QC, G1V 0A6, Canada
Fax: +14186567916; Eꢀmail: thierry.ollevier@chm.ulaval.ca
b
Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshahr, Iran
Fax: +981232211647; Eꢀmail: m.khalilzadeh@hotmail.com

Page 2 of 30
Graphical Abstract
X
O
EWG
DMSO, 110–115 °C
EWG
R
0.1–5 h, X = F, Cl, Br
7
0–100%
CsF/Clinoptilolite
R = H, Halogen, Alkyl, OMe, CN, NO2
OH
R
X
O
H(OMe)
DMSO, 120 °C
OMe
R
14–16 h
7
2–91%
CsF/Clinoptilolite + CuO-np
2

Page 3 of 30
Abstract
CsF/Clinoptilolite (CsF/CP) was found to be an efficient solid base catalyst for both S Ar and Ullmann ether
N
reactions. A general and efficient oneꢀstep procedure was developed for the synthesis of biaryl ethers via direct
coupling of electronꢀdeficient aryl halides to phenols using CsF/CP. The protocol was also applied to electronꢀ
rich aryl halides by addition of a catalytic amount of copper oxide nanoparticles. Both S Ar and Ullmann
N
reactions were rapid and provided good to excellent yields.
Keywords
Diaryl ethers, S Ar, Ullmann reaction, Heterogeneous catalyst, Clinoptilolite
N
Introduction
Zeolites are crystalline threeꢀdimensional aluminosilicates with open channels or cages with molecular
1
dimensions. They are widely used as catalysts in chemical industries, in cracking, isomerization and alkylation
2
processes. Among those having synthetic and natural origin, natural zeolites are of great interest due to their
large scale availability and low prices. However, in spite of their availability, only a few representatives of this
3
class have been reported as solid supports in the field of organic synthesis. As a consequence of confined space
4
inside the porous structure, these materials are able to act as shapeꢀselective nanoreactor, or host cavity for
various metals and small organic compounds. However, the latter is of great interest because the cation
encapsulation of a metal salt catalyst within a cavity might dramatically change its catalytic activity, leading to
unusual increased activity due to the effective cation scavenging. This is the key step, where the anion can act as
5
a Lewis base, accepting an acidic proton. Moreover, solid bases also have the advantages of nontoxicity, ecoꢀ
6
friendliness and easy workꢀup procedure. The importance of the fluoride ion as a catalyst for the promotion of
7
various types of baseꢀcatalyzed reactions in organic synthesis has been previously recognized. In particular, the
work of Miller revealed that the fluoride ion plays an important role in selected reactions because of its high
8
capability of hydrogen bond formation.
3

Page 4 of 30
Cesium fluoride (CsF) is an effective base in organic synthesis because the fluoride ion is largely unreactive
9
as a nucleophile. Removal of silicon groups (desilylation) is one of the major applications of CsF in the
10
laboratory, as its anhydrous nature allows clean formation of waterꢀsensitive intermediates. It is exploited as
11
12
an efficient catalyst for the synthesis of oꢀdiiodoarenes, carboxylic esters, transꢀαꢀtrifluoromethyl allylic
13
14
15
16
alcohols, γꢀlactones, thioesters and thioethers and 3,4ꢀdihydropyrimidineꢀ2ꢀ(1H)ꢀones. In addition, it has
17
18
been used for S ꢀtype aromatic substitution, Michael addition and regioꢀ and chemoselective ring opening of
N
19
20
21
epoxides with thiols, nucleophilic fluorination, selective triflation
and preparation of fluorinated
2
2
polymers. Although being an effective catalyst, it is not easy to handle this hygroscopic product and the
reproducibility of these reactions is invariably poor. Recently, poorly hygroscopic reagents generating fluoride
23
24
25
ions were designed allowing cesium fluoride to be absorbed on Celite, Al O3 and CaO. Although there are
2
26
many reports on the use of solid bases in organic transformations, only a few examples involving S Ar
N
2
7
reactions have been reported. We recently developed a fluorideꢀcatalyzed method for the formation of C–O
28
bonds between activated haloarenes and phenols. In our continued efforts for the development of solid base
catalysts for selective organic transformations, we wish to report herein our development of an improved
catalyst CsF/Clinoptilolite (CsF/CP) as a strong and poorly hygroscopic solid base in organic chemistry. In fact,
when phenol was reacted with 4ꢀfluoronitrobenzene using CsF/CP in DMSO at 110 °C, the desired diaryl ether
was obtained in quantitative isolated yield in short reaction time (0.15 h). This was in agreement with the
29
tendency of clinoptilolite for cation absorption which was reported previously. This result led us to undertake a
survey of reaction variables to develop the optimum conditions for the transformation.
Results and Discussion
Effect of base amount on the coupling reaction
The efficiency of CsF/CP system was studied for the synthesis of 4ꢀnitrophenyl phenyl ether with various
amounts of base (Table 1). At first, a model reaction was carried out in the absence of a base. The reaction of 1a
with 2a did not afford an appreciable amount of the desired 4ꢀnitrophenyl phenyl ether in the absence of CsF
even after the extended time (8 h), whereas, 0.54 g of catalyst involving 60% (w/w) cesium fluoride, afforded
1
00% of conversion after 0.15 h (Table 1, entries 9 and 12). These findings revealed that the heterogeneous
catalyst exhibited high catalytic activity in the desired transformation. Control experiment with unsupported CsF
4

Page 5 of 30
(
(
1 equiv.) at 110 °C showed quantitative conversion of 4ꢀfluoronitrobenzene, albeit after a longer reaction time
Table 1, entry 1). When the quantity of CsF/CP was reduced from 0.54 g (1 equiv.) to 0.45 g (0.83 equiv.), the
yield of the product remained unchanged. However, the required time was longer (Table 1, entry 11). Higher
quantity of CsF/CP did not have great influence on the outcome of the reaction (Table 1, entry 13).
Solvent and temperature effects on the coupling reaction
Some commercial solvents such as acetonitrile, toluene, dioxane, DMF and DMSO were examined (Table
1
). We found that both solvents, DMSO (Table 1, entry 12) and DMF (Table 1, entry 6), are ideal for the
efficient and rapid coupling of phenol and 4ꢀfluoronitrobenzene with comparable efficiency.
Effect of reaction temperature on the coupling reaction of 4ꢀfluoronitrobenzene and phenol using CsF/CP
was studied. As expected, the reaction time was influenced by the temperature. It was found that by increasing
the reaction temperature, the conversion was increased favorably reaching its maximum at 110 °C, whereas,
increasing the reaction temperature to 120 °C had a little effect on the yield of the reaction. The reaction did not
proceed well at room temperature and gave only very poor yields.
a
Table 1 OꢀArylation of Phenol with 4ꢀFluoronitrobenze: Optimization of the Reaction Conditions
<Table 1ꢀScheme>
b
Entry
Base (g)
CsF (0.32 g)
CP (0.22 g)
Solvent
DMSO
DMSO
DMSO
MeCN
Toluene
DMF
Dioxane
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
t (h)
8
8
0.5
5
5
T (°C)
110
110
110
110
Yield (%)
100
<7
100
78
75
98
45
100
100
98
100
100
100
1
2
3
4
5
6
7
8
9
KF/CP (0.62 g)
CsF/CP (0.54 g)
CsF/CP (0.54 g)
CsF/CP (0.54 g)
CsF/CP (0.54 g)
CsF/CP (0.54 g)
CsF/CP (0.54 g)c
CsF/CP (0.54 g)
CsF/CP (0.45 g)
CsF/CP (0.54 g)
CsF/CP (0.65 g)
110
0.75 110
110
4
1.30 90
0.15 120
0.75 110
0.5
0.15 110
0.15 110
1
1
1
1
0
1
2
3
110
a
b
Reaction conditions: Aryl–F (2 mmol), Phenol (2.1 mmol), Solvents (5–7 mL). Average GC yields with nꢀoctane as an
c
internal standard calculated from at least two runs. 2 mmol of phenol was used.
Catalytic activity of powdered CsF/CP with various CsF loadings
The CsF/CP samples were prepared with various loadings of CsF over the support, namely 4, 7.5, 9.5 and
1
0.5 mmol/g. The catalyst with a loading of 9.5 mmol/g displayed the highest activity compared with the other
catalysts, while the catalyst with a loading of 10.5 mmol/g showed almost equal activity in this reaction (Fig. 1).
5

Page 6 of 30
The loss of activity observed above 9.5 mmol/g was possibly due to decreasing quantity of CsF in the CP
cavities or due to CsF aggregation, thus reducing the dispersion of CsF on the zeolite. The catalyst with a
loading of 9.5 mmol CsF/g Clinoptilolite [ca. 60% (w/w) CsF] was chosen for our studies.
<
Insert Fig.1>
In our examination of the use of CsF/CP for the combination of electronꢀpoor aryl halides with a variety of
phenol derivatives, it is clear that aryl halides substituted in the para position with electronꢀwithdrawing groups
can be coupled with a wide diversity of phenols to give the desired product in good to excellent yields (see
Table 2). The fact that these activated aryl halides are particularly good substrates refers to charge stabilization
30
of the intermediate Meisenheimer complex formed during the reaction.
Having established the optimal reaction conditions (CsF/CP 0.54 g, phenol 0.2 g (2.1 mmol) and 4
fluoronitrobenzene 0.28 g (2 mmol) in DMSO), the protocol was extended to other aryl fluorides, chlorides and
bromides to verify scope and limitations of the method (Table 2). The coupling of the 4 fluoronitrobenzene with
moderately electronꢀdeficient halophenols such as iodoꢀ, bromoꢀ and chlorophenols occurred in excellent yields
Table 2, entries 1–9). Even sterically hindered orthoꢀsubstituted phenols reacted with 4 fluoronitrobenzene, and
-
-
(
-
the reaction proceeded smoothly to give the diaryl ethers in excellent yields (Table 2, entries 3, 6 and 7).
Similarly, sterically encumbered nucleophiles such as 2ꢀtertꢀbutylphenol, which is quite problematic as
coupling partners in S Ar reactions, reacted with 4ꢀfluoronitrobenzene to give the corresponding diaryl ether in
N
a 98% yield (Table 2, entry 11). The reaction of sterically hindered 2,6ꢀdiꢀtertꢀbutylphenol with 4
-
fluoronitrobenzene using the standard base system produced no undesired products but the expected product in a
moderate yield and in longer reaction time (Table 2, entry 14). It should be noted that S Ar reactions of aryl
N
fluorides generally proceed readily with electronꢀrich phenols and sluggishly with electronꢀpoor phenols. To our
surprise, using CsF/CP, even phenols bearing an electronꢀwithdrawing group such as nitro and cyano could also
serve as efficient coupling partners (Table 2, entries 17–20).
A variety of substituted phenols were transformed into their corresponding ethers in good to excellent
isolated yields. The protocol tolerates functional groups like halides, methoxy, or carboxylic acid esters. An
aldehyde functional group on an aryl fluoride was also compatible under these conditions, although a slightly
lower yield was obtained in the reaction of 4ꢀfluorobenzaldehyde with phenol (Table 2, entry 25). By routinely
6

Page 7 of 30
running reactions in DMSO at 110 °C, we were able to couple electrophiles containing electronꢀwithdrawing
groups other than nitro. Addition of phenols to aryl fluorides substituted with cyano, esters or formyl were also
feasible provided sufficient reaction times were allowed and a directing substitution pattern (para) employed
(
entries 21–25). However, this protocol provided good yields only for electronꢀdeficient aryl fluorides, chlorides
and bromides. Electronꢀneutral and electronꢀrich aryl halides were not active in our system and afforded only
poor yields
.
a
Table 2 CsF/CP Promoted Coupling of Nitro Activated Aryl Fluorides with Phenols
Table 2ꢀScheme>
<
b
Entry
1
Phenol
Aryl halide
Product
Time (h) Yield (%)
<
Table 2ꢀEntry 1>
0.15
95
<
Table 2ꢀEntry 2>
0
.15
100
2
<
<
<
<
<
<
<
Table 2ꢀEntry 3>
Table 2ꢀEntry 4>
Table 2ꢀEntry 5>
Table 2ꢀEntry 6>
Table 2ꢀEntry 7>
Table 2ꢀEntry 8>
Table 2ꢀEntry 9>
0.15
0.15
0.15
0.15
3
100
100
100
100
100
95
3
4
5
6
7
8
9
0.15
0.15
0.15
0.75
0.5
95
<
<
<
<
<
<
<
Table 2ꢀEntry 10>
Table 2ꢀEntry 11>
Table 2ꢀEntry 12>
Table 2ꢀEntry 13>
Table 2ꢀEntry 14>
Table 2ꢀEntry 15>
Table 2ꢀEntry 16>
95
1
1
1
1
1
1
1
0
1
2
3
4
5
6
98
95
0.15
5
95
78
0.15
100
0
.5
100
80
<
Table 2ꢀEntry 17>
1
7
0.75
7

Page 8 of 30
<
Table 2ꢀEntry 18>
0
.5
98
1
8
<
<
<
<
<
<
Table 2ꢀEntry 19>
Table 2ꢀEntry 20>
Table 2ꢀEntry 21>
Table 2ꢀEntry 22>
Table 2ꢀEntry 23>
Table 2ꢀEntry 24>
0.75
0.5
0.5
0.5
2.5
3.5
98
100
92
1
2
2
2
2
2
9
0
1
2
3
4
92
88
90
<
<
Table 2ꢀEntry 25>
Table 2ꢀEntry 26>
2.5
85
2
2
5
2.5
2
90
85
6
7
<
Table 2ꢀEntry 27>
2
a
b
Reaction conditions: Aryl halide (2 mmol), phenol (2.1 mmol), CsF/CP (0.54 g), DMSO (5–7 mL). Isolated yield.
Comparing superiority of CsF/CP over some previously reported protocols
A comparison of the present protocol with selected previously known protocols is collected in Table 3 to
demonstrate that the present protocol is indeed superior to several of them. Phenol is completely arylated in less
than 0.15 h at 110 °C in 100% isolated yield using the present protocol. Most of the other protocols listed
involve either longer time for completion or require prior preparation of the phenolic nucleophile or use
expensive materials with generally reduced isolated yields.
The present protocol is effective in affording complete arylation of 2ꢀtertꢀbutylphenol in less than 0.75 h.
The same transformation requires 9 h for completion using silylated phenol and proazaphosphatrane (Table 3,
entry 6). 4ꢀtertꢀButylphenol is arylated completely in less than 0.5 h using the present protocol. The use of
Bu NBr/CsF is equally effective, however, it requires a long reaction time. Inspection of Table 2 reveals that
4
31
KFꢀbased reagent gave marginally lower yields than the CsF counterpart with extended reaction times.
Although this difference is small in general cases, it is more pronounced when comparing the coupling reaction
of sterically bulky nucleophiles such as 2,6ꢀdiꢀtertꢀbutylphenol and 2,4,6ꢀtrichlorophenol with 4ꢀ
fluoronitrobenzene (Table 2, entries 7, 14 vs Table 3 entries 8, 9). Overall, the present methodology uses a cheap
and environmentally friendly heterogeneous catalyst and requires relatively shorter reaction times.
8

Page 9 of 30
Table 3 Comparison of Protocols for the Oꢀarylation of Phenolic Nucleophiles with 4ꢀFluoronitrobenzene.
Entry
Phenolic nucleophiles
Si(OPh)
PhOTBS
Phenol
PhOMS
Time (h)
Yield (%)
92
92
98
80
92
99
97
47
Base
Temp. °C
50
100
Ref.
100
MW
80
90
110ꢀ115
110ꢀ115
110
Solvent
3
2
1
2
3
4
5
6
7
8
9
4
24
1
1
18
0.15
9
16
15
6
TBAF
Acetone
33
Cs
KF/Al
CO
KF/Al
2
CO
3
DMF
CH CN
[Bmim]BF
4
27
2
O
3
3
/18ꢀcrownꢀ6
/Aliquatꢀ336
3
3
4
K
2
3
3
5
Phenol
2
O
Solventꢀfree
3
6
2ꢀtꢀBuꢀPhOTBDMS
4ꢀtertꢀbutylphenol
2,4,6ꢀtrichlorophenol
2,6ꢀdiꢀtertꢀbutylphenol
Phenol
Proazaphosphatrane
Bu NBr/CsF
Toluene
3
7
4
scCO
2
(ca.21 MPa)
28
KF/CP
KF/CP
CsF/CP
CsF/CP
CsF/CP
DMSO
DMSO
DMSO
DMSO
DMSO
28
85
100
98
1
1
1
0
1
2
0.15
0.75
0.5
2ꢀtertꢀbutylphenol
4ꢀtertꢀbutylphenol
110
110
95
Reusability of the catalyst
We studied simple ways of recycling the CsF/CP solid base catalyst. The solid base was collected after the
reaction was completed. It was then filtered, washed thoroughly with ethyl acetate to extract the product and
dried at 80 °C in a vacuum drying oven. The activity of the base dropped significantly. The loss might be
+
−
attributed to the leaching of ionic species (Cs , F ) from the catalyst into diaryl ether product mixture, which
was confirmed by flame atomic spectroscopy. An attempt was made to retain the ionic species of the catalyst
using vacuum distillation. The solvent of the reaction mixture was distilled off and the remaining solid was
washed thoroughly with dioxane to remove organic materials. The next run was performed by adding fresh
reactants to the recovered catalyst. Three consecutive reactions were performed in this manner retaining the
ionic species within the catalyst and the results are given in Table 4. The catalyst showed good recycling ability
with slight loss in activity.
Table 4 Recycling of CsF/CP Catalyst for the Oꢀarylation of Phenol with 4ꢀFluoronitrobenzene.
Run
1
2
3
4
Catalyst
Fresh
Recycleꢀ1
Recycleꢀ2
Recycleꢀ3
Conversion (%)
100
96
94
90
In continuation of our research work we were interested in the coupling reaction of phenols with unactivated
aryl halides. Copperꢀcatalyzed Ullmann coupling of aryl halides with phenols represents the most popular
38
choice for the synthesis of diaryl ethers on laboratory and industrial scales. However, the utility of classical
Ullmann coupling has been greatly limited by harsh reaction conditions, for example, high temperatures,
39
stoichiometric use of copper compounds and low conversion of unactivated aryl halides. Although much effort
9

Page 10 of 30
has been devoted to developing more convenient methods of Ullmannꢀtype Oꢀarylation in recent years,
invention of mild, simple and lowꢀcost methods are still highly desirable. Nanoparticles have emerged as robust
40
and high surface area heterogeneous catalysts, which serve as sustainable alternatives to conventional
materials, especially CuO nanoparticles due to their stability and wide availability.
41
Recently, CuO nanoparticle catalyzed C–N, C–O, and C–S crossꢀcoupling reactions have been disclosed.
Following successful application of CuO nanoparticles in phenol etherification, we wish to report a new system
in Ullmann type reaction catalyzed by CuO nanoparticles using CsF/CP as solid base. When the coupling
reaction of phenol with iodobenzene was performed in DMSO at 120 °C in the presence of CsF/CP under inert
atmosphere, the reaction proceeded to completion after 14 hours. Further investigation showed that the reaction
did not proceed at room temperature. Next, we extended our protocol to other phenol derivatives. The results are
summarized in Table 5. Our method compares well with other protocols used for the copper catalyzed Ullmann
43a
43b
reaction (Table 5, entry 1, yield of diphenylether: 91%; with CuBr, 97%; with CuI, 95%; with CuO,
43c
43d
8
7%; with αꢀFe O @CuO 92%).
2
3
42
Copper nanoparticles were prepared according to a previously reported procedure. The morphology of the
CuO nanostructure was characterized by SEM and TEM techniques. Typical SEM micrograph of the CuO
nanoparticle is shown in Figure 2a. Results show the presence of CuO in nanosize. Figure 2b presents a typical
TEM image of CuO nanoparticles. Results show CuO nanoparticles with a diameter of about 25 nm.
<
Insert Fig.2>
The absence of CsF/CP fails to generate the desired products and all the starting materials were recovered
from the reaction system. Decreasing the catalyst loading from 10 to 5 mol % resulted in a decrease of the yield
even under extended reaction time conditions. Moderate to excellent yields were obtained for substituted
phenols with both electronꢀdonating and electronꢀwithdrawing substituents (Table 5).
In general, the presence of electronꢀdonating groups on phenols leads to higher yields than those with phenol
with electronꢀwithdrawing groups. Interestingly, even phenols with more steric hindrance in the ortho position
were tolerated in this reaction (Table 5, entries 4, 6 and 8). The presence of an electronꢀdonating group on the
iodo aryl partner did not have great influence on the outcome of the reaction (Table 5, entries 11 and 12).
10

Page 11 of 30
a
Table 5 Coupling Reaction of Aryl Halides with Phenols using CsF/CP in the Presence of CuOꢀnp Catalyst
b
Entry
Phenols
Aryl iodide
Time
h)
Yield (%)
(
1
2
3
4
<Table 5ꢀEntry 1>
<Table 5ꢀEntry 2>
<Table 5ꢀEntry 3>
<Table 5ꢀEntry 4>
<Table 5ꢀEntry 1>
<Table 5ꢀEntry 2>
<Table 5ꢀEntry 3>
<Table 5ꢀEntry 4>
<Table 5ꢀEntry 5>
14
18
16
20
91
84
80
72
<
Table 5ꢀEntry 5>
5
1
4
91
82
6
7
<Table 5ꢀEntry 6>
<Table 5ꢀEntry 7>
<Table 5ꢀEntry 6>
<Table 5ꢀEntry 7>
<Table 5ꢀEntry 8>
<Table 5ꢀEntry 9>
<Table 5ꢀEntry 10>
1
2
5
6
78
78
<
<
Table 5ꢀEntry 8>
Table 5ꢀEntry 9>
8
9
20
15
15
89
90
<
Table 5ꢀEntry 10>
1
0
<
<
Table 5ꢀEntry 11>
Table 5ꢀEntry 12>
<Table 5ꢀEntry 11>
<Table 5ꢀEntry 12>
1
1
1
2
15
15
87
85
a
Reaction conditions: Phenol (0.75 mmol), CuOꢀnp (10 mol %), Iodobenzene (0.5 mmol), CsF/CP (0.5 g) and DMSO (5
b
mL) at 120 ºC under N2. Isolated yield.
A plausible mechanism of the copperꢀcatalyzed reaction is shown in Scheme 1. As drawn, the catalytic cycle
maybe initiated by abstraction of a proton by a negatively charged fluoride moiety from the phenol to generate
the corresponding anion a stabilized on the cesium surface, which then attacked active species b to afford
intermediate c, where the positive charge developed may be distributed among the CuO nanoparticles present on
the surface of the nanoparticle cluster. Intermediate c may transform to free catalyst d by reductive elimination
providing the C–O cross coupled product followed by removal of hydrogen halide with CsF/CP.
Scheme 1 Proposed mechanism for CuO nanoparticlesꢀcatalyzed Oꢀarylation of phenols with aryl halides
11

Page 12 of 30
Conclusion
We have prepared a nonhygroscopic solid base, CsF/CP, and employed it as an efficient base in the S Ar
N
and Ullmann coupling reactions of phenols with aryl halides. In comparison to cesium fluoride, CsF/CP is a
moisture stable base, which is prepared by a simple procedure and could be stored for extended periods of time
under air or in a desicator without noticeable deactivation. The reaction can be carried out under mild conditions
without any additives, affording the corresponding aryl ethers in good yields via S Ar reaction. CsF/CP also
N
enabled the Ullmannꢀtype Oꢀarylation of phenyl iodides to be performed cleanly. Overall, CsF/CP is a more
28
efficient solid base than our previously reported one (KF/CP). The use of CsF/CP as heterogeneous base in
other reactions is currently in progress in our laboratories.
Acknowledgments
The authors wish to thank the Islamic Azad University, Qaemshahr branch for funding this research, and the
Natural Sciences and Engineering Research Council of Canada (NSERC).
Experimental
General Remarks
The raw material was an Iranian commercial Clinoptilolite (Afrandtooska Company) from deposits in the
region of Semnan (very cheap, about 1$ per kg). All starting materials were used as purchased without further
purification. Reactions were performed under air atmosphere. Thinꢀlayer chromatography (TLC) was performed
using on 60 mesh silica gel Merck TLC plates. Flash column chromatography was performed with Merck silica
gel (230–400 mesh). The yields reported are isolated yields and are the average of at least two runs. All values
were analyzed by using a HP GC 6890 that was equipped with a DBꢀ5 CP column (30 m x 0.32 mm x 0.5 µm).
GC program parameters: injector 250 °C; flow 2 ml/min.; temperature program 40 °C/hold 2 min.; 280 °C/rate
1
0 °C per min./hold 5 min. Melting points were determined using an Electro thermal IA 9100 Digital Melting
Point apparatus and are uncorrected. NMR spectra were recorded on a Bruker AVꢀIIIꢀ600 FTꢀNMR 600 MHz,
12

Page 13 of 30
Bruker FTꢀNMR 400 MHzꢀUltrashild and Bruker FTꢀNMR 300 MHzꢀUltrashild spectrometer. NMR spectra
were obtained in CDCl and DMSOꢀd6.
3
Preparation of CsF/Clinoptilolite
Prepared by dissolving CsF (14.5 g) in distilled water (10 mL) and Clinoptilolite (10 g). The mixture was
stirred for 1 h then, the water was removed at 60–70 °C under reduced pressure (rotary evaporator). The
impregnated Clinoptilolite was further dried at 80 °C in a vacuum drying oven for 30 h. The hard, dry material,
thus obtained (24.5 g), was powdered with the help of a pestle and mortar. The resulting CsF/CP was kept in a
desiccator until required.
Typical Procedure A
Coupling of aryl fluorides with phenols in DMSO: A mixture of phenol (2.1 mmol), Aryl halide (2.0 mmol),
and 60% (w/w) cesium fluoride/Clinoptilolite [CsF/CP] (0.54 g) in DMSO (5–7 mL) was heated at 110 °C (bath
temperature). The mixture was stirred under air until the reaction was complete (monitored by TLC or GC). The
reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered. The resulting solution
was placed in a separating funnel and washed twice with water. The organic layer was dried with anhydrous
sodium sulfate, filtered, and concentrated in vacuo. The crude product was recrystallized in methanol to afford
the final product.
Typical Procedure B
A mixture of the phenol (0.75 mmol), aryl halide (0.5 mmol), CuO nanoparticles (10 mol %) and 60% (w/w)
CsF/CP (0.5 g) in dry DMSO (4 mL) was heated at 120 °C. The mixture was stirred under nitrogen atmosphere
until the reaction was complete (by TLC or GC monitoring). After completion, the reaction mixture was cooled
to room temperature, diluted with ethyl acetate, and filtered. The resulting solution was placed in a separatory
funnel and washed twice with water. The organic layer was dried over anhydrous sodium sulfate, filtered, and
concentrated in vacuo. The crude products were purified by column chromatography on silica gel eluting with
ethyl acetate/hexane mixtures to afford the final product.
44
1
-Fluoro-3-(4-nitrophenoxy)benzene (Table 2, entry 1). Prepared according procedure A, using 3ꢀ
fluorophenol (235 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
3
product (442 mg, 95% yield) as a colorless oil. H NMR (600 MHz, CDCl ): δ 8.24 (d, J = 9.0 Hz, 2H), 7.42
3
HH
13

Page 14 of 30
3
3
3
3
4
(
dd, J = 8.4 Hz, J = 6.8 Hz, 1H), 7.09 (d, J = 9.0 Hz, 2H), 6.97 (dt, J = 6.8 Hz, J = 3.0 Hz, 1H),
HF HH HH HH HF
3
4
3
4
13
6
.89 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 6.84 (td, J = 9.6 Hz, J = 2.4 Hz, 1H) ppm. C NMR (150
HF HH HH HF
1
3
3
MHz, CDCl ): δ 164.6, 162.6 (d, J = 288 Hz), 156.6 (d, J = 36 Hz), 143.3, 131.4 (d, J = 36 Hz), 126.2,
3
CF
CF
CF
4
2
2
1
17.9, 116.0 (d, J = 12 Hz), 112.4 (d, J = 96 Hz), 104.9 (d, J = 102 Hz) ppm.
CF CF CF
45
1
-Fluoro-4-(4-nitrophenoxy)benzene (Table 2, entry 2). Prepared according to procedure A, using 4ꢀ
fluorophenol (235 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (466 mg, 100% yield) as a yellow solid. mp: 59 °C (litt.: 56–58 °C). H NMR (400 MHz, CDCl ): δ
3
3
3
13
8
.18 (d, J = 9.2 Hz, 2H), 7.05ꢀ7.17 (m, 4H), 6.98 (d, J = 9.2 Hz, 2H) ppm. C NMR (100 MHz, CDCl ): δ
HH HH 3
2
3
1
1
63.4, 160.9, 159.3, 150.5 (d, J = 126 Hz), 143.3, 126.2, 122.4 (d, J = 36 Hz), 116.9 (t, J = 222 Hz)
CF CF CF
ppm.
28
1
-Chloro-2-(4-nitrophenoxy)benzene (Table 2, entry 3). Prepared according to procedure A, using 2ꢀ
chlorophenol (330 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product as a (499 mg, 100% yield) as a white solid. mp: 77 °C (litt.: 78–79 °C). H NMR (400 MHz, CDCl ): δ
3
3
3
4
3
4
8
7
2
1
.19 (d, J = 8.9, 2H), 7.51 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.33 (dt, J = 8.0 Hz, J = 1.6 Hz, 1H),
HH HH HH HH HH
3
4
3
4
3
.23 (dt, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.16 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 6.93 (d, J = 8.9 Hz,
HH
HH
HH
HH
HH
H) ppm.
-Chloro-3-(4-nitrophenoxy)benzene (Table 2, entry 4). Prepared according to procedure A, using 3ꢀ
46
chlorophenol (330 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (499 mg, 100% yield) as a white solid. mp: 60 °C (litt.: 60–62 °C). H NMR (600 MHz, CDCl ) δ: 8.24
3
3
3
3
3
4
(
d, J = 9.6 Hz, 2H), 7.36 (dd, J = 8.4 Hz, J = 7.8 Hz, 1H), 7.24 (dd, J = 8.3 Hz, J = 1.8 Hz, 1H),
HH HH HH HH HH
4
4
3
3
4
7
1
.11 (dd, J = 2.4 Hz, J = 1.8 Hz, 1H), 7.05 (d, J = 9.6 Hz, 2H), 6.99 (dd, J = 8.3 Hz, J = 1.8 Hz,
HH HH HH HH HH
1
3
H) ppm. C NMR (150 MHz, CDCl ): δ 163.1, 156.3, 144.2, 136.1, 131.4, 126.2, 125.1, 121.3, 119.3, 118.5
3
ppm.
-Fluoro-4-(4-nitrophenoxy)benzene (Table 2, entry 5). Prepared according to procedure A, using 4ꢀ
chlorophenol (330 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
47
1
14

Page 15 of 30
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (499 mg, 100% yield) as a white solid. mp: 76 °C (litt.: 76–78 °C). H NMR (400 MHz, CDCl ): δ 8.20
3
3
3
3
3
(
dd, J = 7.0 Hz, J = 2.4 Hz, 2H), 7.38 (d, J = 7.0 Hz, J = 2.4 Hz, 2H), 6.92
–
7.13 (m, 4H) ppm.
HH
HH
HH
HH
28
2
,4-Dichloro-1-(4-nitrophenoxy)benzene (Table 2, entry 6). Prepared according to procedure A, using 2,4ꢀ
dichlorophenol (342 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g)
in DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (568 mg, 100% yield) as a white solid. mp: 73 °C (litt.: 72–73 °C). H NMR (300 MHz, DMSOꢀd6): δ
3
4
3
4
8
.25 (d, J = 9.1 Hz, 2H), 7.87 (d, J = 1.9 Hz, 1H), 7.56 (dd, J = 8.7 Hz, J = 1.9 Hz, 1H), 7.42 (d,
HH HH HH HH
3
3
13
JHH = 8.7 Hz, 1H), 7.13 (d, J = 9.1 Hz, 2H) ppm. C NMR (75 MHz, DMSOꢀd6): δ 162.2, 149.0, 143.1,
HH
1
31.2, 131.0, 129.9, 127.4, 126.7, 125.0, 117.2 ppm.
28
1
,3,5-Trichloro-2-(4-nitrophenoxy)benzene (Table 2, entry 7). Prepared according to procedure A, using
2
,4,6ꢀtrichlorophenol (414 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP
(
0.54 g) in DMSO (5 mL) at 110 °C. After 3 h, the crude product was recrystallized in methanol to afford the
1
final product (637 mg, 100% yield) as a yellow solid. mp: 94 °C (litt.: 93–95 °C). H NMR (300 MHz, DMSOꢀ
3
3
13
d6): δ 8.24 (d, J = 8.9 Hz, 2H), 7.94 (s, 2H), 7.14 (d, J = 8.9 Hz, 2H) ppm. C NMR (75 MHz, DMSOꢀ
HH
HH
d6): δ 161.0, 144.9, 143.4, 132.1, 130.2, 129.7, 126.8, 116.0 ppm.
28
1
-Bromo-4-(4-nitrophenoxy)benzene (Table 2, entry 8). Prepared according to procedure A, using 4ꢀ
bromophenol (363 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g)
in DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (558 mg, 95% yield) as a light yellow solid. mp: 58 °C (litt.: 58–60 °C). H NMR (300 MHz, DMSOꢀ
3
3
3
13
d6): δ 8.24 (d, J = 9.1 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 7.14 (d, J = 9.1 Hz, 4H) ppm. C NMR (75
HH
HH
HH
MHz, DMSOꢀd6): δ 162.8, 154.2, 143.0, 133.8, 126.6, 123.1, 118.1, 117.9 ppm.
4
8
1
-Iodo-4-(4-nitrophenoxy)benzene (Table 2, entry 9). Prepared according to procedure A, using 4ꢀ
iodophenol (462 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (647 mg, 95% yield) as a yellow solid. mp: 51 ºC (litt.: 50–52 °C). H NMR (400 MHz, CDCl ): δ 8.22
3
15

Page 16 of 30
3
3
3
3
(
d, J = 9.2 Hz, 2H), 7.75 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 9.2 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H) ppm.
HH HH HH HH
13
C NMR (100 MHz, CDCl ): δ 163.2, 155.0, 143.7, 139.4, 126.3, 123.2, 117.0, 89.4 ppm.
3
28
1
-Methyl-4-(4-nitrophenoxy)benzene (Table 2, entry 10). Prepared according to procedure A, using 4ꢀ
methylphenol (227 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g)
in DMSO (5 mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final
1
product (435 mg, 95% yield) as an orange solid. mp: 69 °C (litt.: 69–70 °C). H NMR (300 MHz, DMSOꢀd6): δ
3
3
3
13
8
.22 (d, J = 9.2 Hz, 2H), 7.28 (d, J = 8.2 Hz, 2H), 7.06 (d, J = 8.8 Hz, 4H), 2.33 (s, 3H) ppm. C NMR
HH HH HH
(
75 MHz, DMSOꢀd6): δ 163.7, 152.3, 142.4, 135.3, 131.3, 126.6, 120.9, 117.4, 20.8 ppm.
46
1
-(tert-Butyl)-2-(4-nitrophenoxy)benzene (Table 2, entry 11). Prepared according to procedure A, using 2ꢀ
tertꢀbutylphenol (315 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54
g) in DMSO (5 mL) at 110 °C. After 0.75 h, the crude product was recrystallized in methanol to afford the final
1
product (531 mg, 98% yield) as a white solid. mp: 106 °C (litt.: 105–107 °C). H NMR (400 MHz, CDCl ): δ
3
3
3
3
3
8
.22 (d, J = 8.1 Hz, 2H), 7.49 (d, J = 7.8 Hz, 1H), 7.23 (m, 2H), 7.03 (d, J = 8.1 Hz, 2H), 6.91 (d, J
HH HH HH HH
13
=
7.8 Hz, 1H), 1.41 (s, 9H) ppm. C NMR (100 MHz, CDCl ): 163.8, 153.6, 142.9, 142.2, 128.3, 127.6, 126.7,
3
1
25.7, 121.6, 117.6, 35.2, 30.1 ppm.
-(tert-Butyl)-4-(4-nitrophenoxy)benzene (Table 2, entry 12). Prepared according to procedure A, using 4ꢀ
49
1
tertꢀbutylphenol (315 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54
g) in DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the final
1
3
product (514 mg, 95% yield) as a white solid. H NMR (300 MHz, CDCl ): δ 8.18 (d, J = 9.3 Hz, 2H), 7.42
3
HH
3
3
3
(
d, J = 9.3 Hz, 2H), 7.02 (d, J = 2.7 Hz, 2H), 6.99 (d, J = 2.7 Hz, 2H), 1.35 (s, 9H) ppm.
HH HH HH
4
5
1
3
,3-Dimethyl-5-(4-nitrophenoxy)benzene (Table 2, entry 13). Prepared according to procedure A, using
,5ꢀdimethylphenol (256 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP
(
0.54 g) in DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the
1
final product (461 mg, 95% yield) as a yellow solid. mp: 78 °C (litt.: 77–78 °C). H NMR (600 MHz, CDCl ): δ
3
3
3
13
8
.2 (d, J = 9.6 Hz, 2H), 7.01 (d, J = 9.6 Hz, 2H), 6.9 (brs, 1H), 6.7 (brs, 2H), 2.3 (s, 6H) ppm. C NMR
HH HH
(
150 MHz, CDCl ): 163.8, 154.9, 140.3, 127.4, 125.9, 118.3, 117.2, 113.2, 21.9 ppm.
3
4
6
1
2
,3-Di-tert-butyl-2-(4-nitrophenoxy)benzene (Table 2, entry 14). Prepared according to procedure A, using
,6ꢀdiꢀtertꢀbutylphenol (433 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP
16

Page 17 of 30
(
0.54 g) in DMSO (5 mL) at 110 °C. After 5 h, the crude product was recrystallized in methanol to afford the
1
final product (510 mg, 78% yield) as a yellow solid. mp: 107 °C (litt.: 106–108 °C). H NMR (400 MHz,
3
3
3
3
CDCl ): δ 8.2 (d, J = 9.2 Hz, 2H), 6.98 (d, J = 9.2 Hz, 2H), 6.92 (t, J = 8.8 Hz, 1H), 6.71 (d, J = 8.8
3
HH
HH
HH
HH
13
Hz, 2H), 2.06 (s, 18H) ppm. C NMR (CDCl ): δ 170.4, 164.5, 146.3, 144.2, 125.9, 121.9, 116.3, 116.2, 29.7,
3
2
1.0 ppm.
-(4-Nitrophenoxy)naphthalene (Table 2, entry 15). Prepared according to procedure A, using 2ꢀnaphthol
28
2
(
302 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5
mL) at 110 °C. After 0.15 h, the crude product was recrystallized in methanol to afford the final product (530
1
3
mg, 100% yield) as a red solid. mp: 97 °C (litt.: 98–99 °C). H NMR (600 MHz, CDCl ): δ 8.2 (d, J = 9.0 Hz,
3
HH
3
3
3
2
H), 7.94 (d, J = 9.0 Hz, 2H), 7.80 (d, J = 7.8 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.56 (m, 2H), 7.19 (d,
HH HH HH
3
3
13
JHH = 7.8 Hz, 1H), 7.03 (d, J = 8.1 Hz, 1H) ppm. C NMR (150 MHz, CDCl ): 164.1, 150.5, 142.8, 135.9,
HH
3
1
28.8, 127.8, 127.1, 126.8, 126.3, 126.1, 126.0, 121.9, 116.9, 116.2 ppm.
46
1
-Methoxy-4-(4-nitrophenoxy)benzene (Table 2, entry 16). Prepared according to procedure A, using 4ꢀ
methoxyphenol (260 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g)
in DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the final
1
3
product (490 mg, 100% yield) as a white solid. H NMR (300 MHz, CDCl ): δ 8.18 (d, J = 9.2 Hz, 2H), 7.32
3
HH
3
3
3
13
(
d, J = 8.7 Hz, 2H), 7.02 (d, J = 9.2 Hz, 2H), 6.99 (d, J = 8.7 Hz, 2H), 3.84 (s, 3H) ppm. C NMR (75
HH HH HH
MHz, CDCl ): 164.2, 157.4, 148.2, 142.6, 126.2, 122.4, 116.4, 115.5, 60.1 ppm.
3
47
1
-Nitro-2-(4-nitrophenoxy)benzene (Table 2, entry 17). Prepared according to procedure A, using 2ꢀ
nitrophenol (292 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.75 h, the crude product was recrystallized in methanol to afford the final
1
product (416 mg, 80% yield) as a yellow solid. mp: 94 °C (litt.: 94–95 °C). H NMR (400 MHz, CDCl ): δ 8.26
3
3
3
3
3
(
d, J = 9.6 Hz, 2H), 8.1 (d, J = 8.0 Hz, 1H), 7.71 (t, J = 8.0 Hz, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.26
HH HH HH HH
3
3
13
(
d, J = 8.0 Hz, 1H), 7.05 (d, J = 9.6 Hz, 2H) ppm. C NMR (100 MHz, CDCl ): δ 162.0, 147.7, 143.4,
HH HH 3
1
1
42.3, 134.9, 126.3, 126.1, 122.5, 117.1 ppm.
-Nitro-3-(4-nitrophenoxy)benzene (Table 2, entry 18). Prepared according to procedure A, using 3ꢀ
50
nitrophenol (292 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the final
17

Page 18 of 30
1
product (509 mg, 98% yield) as a yellow solid. mp: 123 °C (litt.: 122–123 °C). H NMR (400 MHz, CDCl ): δ
3
3
3
4
4
3
8
8
.3 (d, J = 9.2 Hz, 2H), 8.13 (dd, J = 8.4 Hz, J = 2.0 Hz, 1H), 7.96 (t, J = 2.0 Hz, 1H), 7.64 (t, J
=
HH
HH
HH
HH
HH
3
4
3
13
.4 Hz, 1H), 7.46 (dd, J = 8.4 Hz, J = 2.0 Hz, 1H), 7.13 (d, J = 9.2 Hz, 2H) ppm. C NMR (100 MHz,
HH
HH
HH
CDCl ): δ 161.5, 155.8, 131.0, 126.3, 126.0, 119.8, 118.2, 115.0 ppm.
3
4
7
4
-(4-Nitrophenoxy)nitrobenzene (Table 2, entry 19). Prepared according to procedure A, using 4ꢀ
nitrophenol (292 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.75 h, the crude product was recrystallized in methanol to afford the final
1
product (509 mg, 98% yield) as a yellow solid. mp: 145 ºC (litt.: 144–146 °C). H NMR (400 MHz, CDCl ): δ
3
8
.15–8.25 (m, 4H), 7.09–7.18 (m, 4H) ppm.
-(4-Nitrophenoxy)benzonitrile (Table 2, entry 20). Prepared according to procedure A, using 4ꢀ
46
4
cyanophenol (250 mg, 2.1 mmol), 4ꢀfluoronitrobenzene (282 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in
DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the final
1
3
product (480 mg, 100% yield) as a yellow solid. H NMR (300 MHz, CDCl ): δ 8.29 (d, J = 9.4 Hz, 2H),
3
HH
3
13
7
1
4
.58 (d, J = 8.6 Hz, 2H), 7.05–7.14 (m, 4H) ppm. C NMR (75 MHz, CDCl ): δ 163.1, 160.2, 145.2, 135.8,
HH 3
26.5, 120.2, 119.3, 118.5, 108.7 ppm.
45
-Phenoxybenzonitrile (Table 2, entry 21). Prepared according to procedure A, using phenol (197 mg, 2.1
mmol), 4ꢀfluorobenzonitrile (242 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5 mL) at 110 °C.
After 0.5 h, the crude product was recrystallized in methanol to afford the final product (358 mg, 92% yield) as
1
a colorless oil. H NMR (400 MHz, CDCl ): δ 7.51–7.63 (m 2H), 7.34–7.44 (m, 2H), 7.16–7.25 (m, 1H), 7.01–
3
1
3
7
1
4
.09 (m, 2H), 6.93ꢀ6.99 (m, 2H) ppm. C NMR (100 MHz, CDCl ): δ 161.6, 154.9, 134.0, 130.3, 125.2, 120.5,
3
18.9, 117.9, 105.8 ppm.
45
-(4-Methoxyphenoxy)benzonitrile (Table 2, entry 22). Prepared according to procedure A, using 4ꢀ
methoxyphenol (260 mg, 2.1 mmol), 4ꢀfluorobenzonitrile (242 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g)
in DMSO (5 mL) at 110 °C. After 0.5 h, the crude product was recrystallized in methanol to afford the final
1
product (414 mg, 92% yield) as a white solid. mp: 101 °C (litt.: 100–101 °C). H NMR (400 MHz, CDCl ): δ
3
13
7
1
.53 (m, 2H), 6.99 (m, 2H), 6.90 (m, 4H), 3.79 (s, 3H) ppm. C NMR (100 MHz, CDCl ): δ 162.3, 156.9,
3
47.8, 134.0, 121.8, 119.0, 117.1, 115.2, 105.2, 55.4 ppm.
18

Page 19 of 30
46
Ethyl 4-(4-methoxyphenoxy)benzoate (Table 2, entry 23). Prepared according to procedure A, using 4ꢀ
methoxyphenol (260 mg, 2.1 mmol), ethyl 4ꢀfluorobenzoate (336 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54
g) in DMSO (5 mL) at 110 °C. After 2.5 h, the crude product was recrystallized in methanol to afford the final
1
3
product (479 mg, 88% yield) as a white solid. H NMR (400 MHz, CDCl ): δ 7.85 (d, J = 8.2 Hz, 2H), 7.10
3
HH
3
3
3
(
d, J = 8.6 Hz, 2H), 6.85 (m, 4H), 4.32 (q, J = 6.5 Hz, 2H), 3.90 (s, 3H), 1.42 (t, J = 6.5 Hz, 3H) ppm.
HH HH HH
13
C NMR (100 MHz, CDCl ): δ 166.5, 163.1, 156.6, 149.1, 132.0, 124.7, 122.2, 116.6, 115.1, 61.3, 56.4, 14.7
3
ppm.
46
Ethyl 4-phenoxybenzoate (Table 2, entry 24). Prepared according to procedure A, using phenol (197 mg, 2.1
mmol), ethyl 4ꢀfluorobenzoate (336 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5 mL) at 110
°C. After 3.5 h, the crude product was recrystallized in methanol to afford the final product (436 mg, 90% yield)
1
as a white solid. H NMR (400 MHz, CDCl ): δ 7.85–8.01 (m, 2H), 7.41ꢀ7.47 (m, 2H), 7.10–7.16 (m, 2H),
3
3
3
13
7
.01–7.05 (m, 2H), 6.91–6.97 (m, 2H), 4.25 (q, J = 6.8 Hz, 2H), 1.41 (t, J = 6.8 Hz, 3H) ppm. C NMR
HH HH
(
100 MHz, CDCl ): δ 165.7, 162.1, 156.7, 131.5, 130.2, 124.7, 124.1, 60.8, 15.2 ppm.
3
51
4
-Phenoxybenzaldehyde (Table 2, entry 25). Prepared according to procedure A, using phenol (197 mg, 2.1
mmol), 4ꢀfluorobenzaldehyde (248 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5 mL) at 110 °C.
After 2.5 h, the crude product was recrystallized in methanol to afford the final product (337 mg, 85% yield) as
1
3
3
a colorless liquid. H NMR (400 MHz, CDCl ): δ 9.92 (s, 1H), 7.68 (d, J = 8.6 Hz, 2H), 7.41 (d, J = 7.8
3
HH
HH
3
13
Hz, 2H), 7.21 (t, J = 8.2 Hz, 1H), 6.99 (m, 4H) ppm. C NMR (100 MHz, CDCl ): δ 191.2, 163.1, 156.2,
HH
3
1
1
2
31.6, 131.0, 130.1, 125.2, 120.6, 117.7 ppm.
45
-Nitro-4-phenoxybenzene (Table 2, entry 26). Prepared according to procedure A, using 4ꢀphenol (197 mg,
.1 mmol), 4ꢀchloronitrobenzene (315 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5 mL) at 110
°C. After 2.5 h, the crude product was recrystallized in methanol to afford the final product (387 mg, 90% yield)
1
3
as a yellow solid. mp: 54 °C (litt.: 54–55 °C). H NMR (400 MHz, CDCl ): δ 7.02 (d, J = 9.1 Hz, 2H), 7.10
3
HH
3
3
3
3
13
(
d, J = 8.0 Hz, 2H), 7.25 (t, J = 7.2 Hz, 1H), 7.44 (t, J = 7.2 Hz, 2H), 8.20 (d, J = 9.1 Hz, 2H). C
HH HH HH HH
NMR (100 MHz, CDCl ): δ 162.5, 153.8, 141.7, 129.5, 125.1, 124.6, 119.7, 116.2 ppm.
3
45
1
-Nitro-4-phenoxybenzene (Table 2, entry 27). Prepared according to procedure A, using 4ꢀphenol (197 mg,
.1 mmol), 4ꢀbromonitrobenzene (404 mg, 2.0 mmol), and 60% (w/w) CsF/CP (0.54 g) in DMSO (5 mL) at 110
2
°C. After 2.5 h, the crude product was recrystallized in methanol to afford the final product (365 mg, 85% yield)
19

Page 20 of 30
1
3
as a yellow solid. mp: 54 °C (litt.: 54–55 °C). H NMR (400 MHz, CDCl ): δ 8.20 (d, J = 9.1 Hz, 2H), 7.45
3
HH
3
3
3
3
13
(
t, J = 7.2 Hz, 2H), 7.26 (t, J = 7.2 Hz, 1H), 7.10 (d, J = 8.0 Hz, 2H), 7.02 (d, J = 9.1 Hz, 2H). C
HH HH HH HH
NMR (100 MHz, CDCl ): δ 162.5, 153.8, 141.7, 129.5, 126.1, 124.6, 119.7, 116.2 ppm.
3
51
Diphenylether (Table 5, entry 1). Prepared according to procedure B, using phenol (71 mg, 0.75 mmol),
iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at 120 °C. After 14 h, the
reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered. The resulting solution
was placed in a separatory funnel and washed twice with water. The organic layer was dried over anhydrous
sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by column
chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (77 mg, 91%
1
yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.37–7.26 (m, 4H), 7.02–7.10 (m, 2H), 6.94–7.03
3
1
3
(
m, 4H) ppm. C NMR (100 MHz, CDCl ): δ 157.1, 129.7, 123.1, 118.8 ppm.
3
5
1
2
0
-Phenoxynaphthalene (Table 5, entry 2). Prepared according to procedure B, using 2ꢀnaphthol (108 mg,
.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at 120 °C.
After 18 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered. The
resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was dried
over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by column
chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (93 mg, 84%
1
yield) as a white solid. mp: 46 ºC (litt.: 45–47 °C). H NMR (300 MHz, CDCl ): δ 7.75–7.81(m, 2H), 7.62–7.69
3
3
13
(
d, J = 7.7 Hz, 1H), 7.25–7.38 (m, 6H), 7.01–7.11 (m, 3H) ppm. C NMR (75 MHz, CDCl ): δ 157.0, 154.9,
HH 3
1
1
34.2, 130.0, 129.7, 129.6, 127.6, 127.0, 126.4, 124.5, 123.3, 119.0, 119.8, 118.0, 113.9 ppm.
51
-Chloro-4-phenoxybenzene (Table 5, entry 3). Prepared according to procedure B, using 4ꢀchlorophenol
(
118 mg, 0.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at
20 °C. After 16 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered.
1
The resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was
dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by
column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (82
1
mg, 80% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.23–7.35 (m, 4H), 7.09–7.13 (m, 1H),
3
20

Page 21 of 30
1
3
6
.90–7.09 (m, 4H) ppm. C NMR (100 MHz, CDCl ): δ 156.8, 155.9, 129.8, 129.6, 128.1, 123.6, 120.0, 118.9
3
ppm.
-Chloro-2-phenoxybenzene (Table 5, entry 4). Prepared according to procedure B, using 2ꢀchlorophenol
118 mg, 0.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at
20 °C. After 20 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered.
51
1
(
1
The resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was
dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by
column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (74
1
3
4
mg, 72% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.45 (dt, J = 7.9 Hz, J = 1.5 Hz, 1H),
3
HH
HH
1
3
7
1
1
.27–7.35 (m, 2H), 7.18–7.22 (m, 1H), 7.04–7.11 (m, 2H), 6.92–7.01 (m, 3H). C NMR (100 MHz, CDCl ): δ
3
56.9, 152.4, 130.7, 129.7, 127.8, 125.8, 124.6, 123.3, 120.8, 117.8 ppm.
51
-Methyl-4-phenoxybenzene (Table 5, entry 5). Prepared according to procedure B, using 4ꢀmethylphenol
(
81 mg, 0.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at
20 °C. After 14 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered.
1
The resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was
dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by
column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (84
1
mg, 91% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.24–7.32 (m, 2H), 7.08–7.15 (m, 2H),
3
1
3
7
1
1
.03–7.08 (m, 1H), 6.93–6.99 (m, 2H), 6.85–6.91 (m, 2H), 2.32 (s, 3H). C NMR (100 MHz, CDCl ): δ 157.8,
3
54.7, 132.8, 130.2, 129.6, 122.7, 119.1, 118.3, 20.6 ppm.
51
-Methyl-2-phenoxybenzene (Table 5, entry 6). Prepared according to procedure B, using 2ꢀmethylphenol
(
81. mg, 0.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at
20 °C. After 15 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered.
1
The resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was
dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by
column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (76
1
mg, 82% yield) as a colorless oil. H NMR (400 MHz, CDCl ): δ 7.29–7.35 (m, 3H), 7.18–7.22 (m, 1H), 7.02–
3
21

Page 22 of 30
1
3
7
1
4
0
.11 (m, 2H), 6.88–6.97 (m, 3H), 2.26 (s, 3H). C NMR (100 MHz, CDCl ): δ 157.7, 154.3, 131.3, 129.8,
3
29.5, 126.9, 123.9, 122.1, 119.6, 117.1, 16.0 ppm.
45
-Phenoxybenzonitrile (Table 5, entry 7). Prepared according to procedure B, using 4ꢀcyanophenol (89 mg,
.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at 120 °C.
After 26 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered. The
resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was dried
over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by column
chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (76 mg, 78%
1
yield) as a colorless oil. H NMR (400 MHz, CDCl ): δ 7.52–7.59 (m, 2H), 7.34–7.41 (m, 2H), 7.18–7.23 (m,
3
1
3
1
1
1
H), 7.03–7.09 (m, 2H), 6.96–7.02 (m, 2H) ppm. C NMR (100 MHz, CDCl ): δ 161.5, 154.8, 134.2, 130.3,
3
25.1, 120.4, 118.9, 117.9, 105.9 ppm.
52
-Methoxy-2-phenoxybenzene (Table 5, entry 8). Prepared according to procedure B, using 2ꢀ
methoxyphenol (93 mg, 0.75 mmol), Iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in
DMSO (4 mL) at 120 °C. After 20 h, the reaction mixture was cooled to room temperature, diluted with ethyl
acetate, and filtered. The resulting solution was placed in a separatory funnel and washed twice with water. The
organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products
were purified by column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the
1
final product (78 mg, 78% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.38–7.42 (m, 2H), 7.12–
3
1
3
7
1
1
.18 (m, 1H), 6.92–7.01 (m, 2H), 6.81–7.02 (m, 2H), 3.77 (s, 3H) ppm. C NMR (100 MHz, CDCl ): δ 158,
3
51.6, 145.1, 129.6, 124.6, 122.6, 121.2, 121.1, 117.3, 112.9, 56.0 ppm.
51
-Methoxy-4-phenoxybenzene (Table 5, entry 9). Prepared according to procedure B, using 4ꢀ
methoxyphenol (93 mg, 0.75 mmol), Iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in
DMSO (4 mL) at 120 °C. After 15 h, the reaction mixture was cooled to room temperature, diluted with ethyl
acetate, and filtered. The resulting solution was placed in a separatory funnel and washed twice with water. The
organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products
were purified by column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the
1
final product (89 mg, 89% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.15–7.28 (m, 2H), 6.80–
3
22

Page 23 of 30
1
3
7
1
1
.10 (m, 7H), 3.77 (s, 3H). C NMR (100 MHz, CDCl ): δ 158.4, 150.0, 155.7, 122.3, 129.7, 120.7, 117.5,
3
14.7, 55.4 ppm.
51
-(tert-Butyl)-4-phenoxybenzene (Table 5, entry 10). Prepared according to procedure B, using 4ꢀ
tertbutylphenol (113 mg, 0.75 mmol), iodobenzene (102 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in
DMSO (4 mL) at 120 °C. After 15 h, the reaction mixture was cooled to room temperature, diluted with ethyl
acetate, and filtered. The resulting solution was placed in a separatory funnel and washed twice with water. The
organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products
were purified by column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the
1
final product (102 mg, 90% yield) as a colorless oil. H NMR (300 MHz, CDCl ): δ 7.37–7.47 (m, 4H), 7.07–
3
1
3
7
1
1
0
1
.14 (m, 2H), 7.03–7.10 (m, 3H), 1.35 (s, 9H) ppm. C NMR (75 MHz, CDCl ): δ 157.4, 154.5, 145.8, 129.5,
3
26.4, 122.7, 118.4, 118.3, 34.1, 31.3 ppm.
51
-Methoxy-4-phenoxybenzene (Table 5, entry 11). Prepared according to procedure B, using phenol (71 mg,
.75 mmol), 4ꢀmethoxyiodobenzene (117 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50 g) in DMSO (4 mL) at
20 °C. After 15 h, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered.
The resulting solution was placed in a separatory funnel and washed twice with water. The organic layer was
dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude products were purified by
column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to afford the final product (87
1
mg, 87% yield) as a colorless liquid. H NMR (400 MHz, CDCl ): δ 7.15–7.28 (m, 2H), 6.80–7.10 (m, 7H),
3
13
3
.77 (s, 3H) ppm. C NMR (100 MHz, CDCl ): δ 158.4, 150.0, 155.7, 122.3, 129.7, 120.7, 117.5, 114.7, 55.4
3
ppm.
,4'-Oxybis(methoxybenzene) (Table 5, entry 12). Prepared according to procedure B, using 4ꢀ
46
4
methoxyphenol (93 mg, 0.75 mmol), 4ꢀmethoxyiodobenzene (117 mg, 0.5 mmol), and 60% (w/w) CsF/CP (0.50
g) in DMSO (4 mL) at 120 °C. After 15 h, the reaction mixture was cooled to room temperature, diluted with
ethyl acetate, and filtered. The resulting solution was placed in a separatory funnel and washed twice with water.
The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude
products were purified by column chromatography on silica gel eluting with ethyl acetate/hexane mixtures to
1
3
afford the final product (98 mg, 85% yield). H NMR (400 MHz, CDCl ): δ 6.92 (d, J = 9.1 Hz, 4H), 6.85 (d,
3
HH
3
13
JHH = 9.1 Hz, 4H), 3.79 (s, 6H) ppm. C NMR (100 MHz, CDCl ): δ 155.3, 151.6, 119.5, 114.7, 55.7 ppm.
3
23

Page 24 of 30
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25

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Fig. 1 Activity of CsF/CP with various loadings of CsF: (♦) 4 mmol/g, (■) 7.5 mmol/g, (×) 9.5 mmol/g and (▲) 10.5
mmol/g.
Fig. 2 SEM (a) and TEM (b) images of nanoꢀCuO particles.
(a)
(b)
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