Cross-coupling reactions of aryl halides with amines, phenols, and thiols catalyzed by an N,N′-dioxide-copper(I) catalytic system

Article abstract of DOI:10.1002/ejoc.201100274

The coupling reactions of various N, O, and S nucleophilic reagents with aryl halides have been successfully carried out under mild conditions by using a novel chiral N,N′-dioxide-copper(I) catalytic system as the catalyst. This versatile and efficient catalyst system has been demonstrated to facilitate the cross-coupling reactions of aryl halides with amines, phenols, and thiols to afford the corresponding desired products in good to excellent yields.

Full text of DOI:10.1002/ejoc.201100274

FULL PAPER
DOI: 10.1002/ejoc.201100274
Cross-Coupling Reactions of Aryl Halides with Amines, Phenols, and Thiols
Catalyzed by an N,NЈ-Dioxide–Copper(I) Catalytic System
Haitao Yang,[a] Chao Xi,[a] Zhiwei Miao,*[a] and Ruyu Chen*[a]
Keywords: Arylation / Copper / Cross-coupling / Nucleophilic substitution / O ligands
The coupling reactions of various N, O, and S nucleophilic
reagents with aryl halides have been successfully carried out
under mild conditions by using a novel chiral N,NЈ-dioxide–
copper(I) catalytic system as the catalyst. This versatile and
efficient catalyst system has been demonstrated to facilitate
the cross-coupling reactions of aryl halides with amines,
phenols, and thiols to afford the corresponding desired prod-
ucts in good to excellent yields.
ligands for facilitating these coupling reactions under rela-
tively mild conditions are still in demand. Herein, we report
that, promoted by N,NЈ-dioxide/CuI catalytic systems, aryl
halides could successfully couple with N-, O-, and S-nucleo-
philic reagents at 80 °C.
Introduction
The transition-metal-catalyzed Ullmann-type coupling
of aryl halides with various nucleophilic compounds is one
of the most important methods for the formation of C-
(aryl)–N, C(aryl)–O, and C(aryl)–S bonds.[1] Nucleophilic
aromatic substitution with aryl halides can be mediated by
palladium,[2] nickel,[3] or copper catalysts.[4] The lower cost
of copper-based catalytic systems makes them particularly
attractive for use in large-scale industrial applications. Re-
cently, additional ligands were deliberately used to facilitate
the copper-catalyzed N-arylation of amines/amides, the O-
arylation of phenols, and the S-arylation of thiols, and sig-
nificant progress has been made.[5–7] Among the different
kinds of multidentate chelating ligands used, the utilization
of some special bidentate additives appear in the majority
of the copper-catalyzed coupling reaction protocols.[8]
However, only a few examples have been reported in which
a general ligand can be used in copper-catalyzed carbon–
heteroatom (N, O, S) and/or aryl–carbon bond formation
in cross-coupling reactions.[8f,9] For example, Venkataraman
and co-workers have developed a mild protocol for the for-
mation of aryl–nitrogen, aryl–oxygen, and aryl–acetylene
bonds using copper–phenanthroline complexes as cata-
lysts.[9a] Fu and co-workers reported a new bidentate ligand,
pyrrolidine-2-phosphonic acid phenyl monoester, for the
copper-catalyzed formation of Ar–N, Ar–O, and Ar–P
bonds.[9b] Recently, Cook and co-workers reported 2-pyr-
idin-2-yl-1H-benzoimidazole as a versatile bidentate N-do-
nor ligand for copper-catalyzed vinyl Ar–N and Ar–O bond
formation.[6a] Therefore, more efficient, versatile, and facile
Results and Discussion
Copper-Catalyzed N-Arylation Reactions
The ligands L1–L6 were synthesized according to known
literature methods (Figure 1).[10] Next, we tried to find the
optimal ligand from compounds L1–L6 for CuI-catalyzed
C–N bond formation. The search for suitable ligands for
imidazole N-arylation with iodobenzene was undertaken in
dioxane at 80 °C with caesium carbonate as base (2 equiv.),
a catalytic amount of cuprous iodide (10 mol-%), and
10 mol-% of each ligand with a reaction time fixed at 20 h.
The results are shown in Table 1. Initially the amide ligand
L1 was employed in this Ullmann reaction. However, only
a trace amount of the product was detected (Table 1, En-
try 1). The CuI/L2 catalytic system catalyzed the reaction
with promising reactivity, giving a yield of 48%, and N-
oxide ligand L3 with a bulky isopropyl group gave a better
yield (Table 1, Entries 2 and 3). Encouraged by this result,
other amines and N,NЈ-dioxide ligands with a chiral back-
bone were investigated. When diamide ligand L4 was em-
ployed, the reaction did not take place, which shows that
the N-oxide group is essential for the reaction (Table 1, En-
try 4). Subsequently, ligands L5 and L6 were examined. By
coordination with CuI, the chiral N,NЈ-dioxide ligand L5
derived from l-proline catalyzed the arylation reaction of
iodobenzene (1a) and produced 1-phenyl-1H-imidazole (3a)
in 82% yield (Table 1, Entry 5). Compared with L5, use of
ligand L6 with a C2 linkage led to a slight decrease in yield
(Table 1, Entry 6). Note that N,NЈ-dioxides can coordinate
with various metal ions and exhibit great potential in many
[a] State Key Laboratory and Institute of Elemento-Organic
Chemistry, Nankai University,
Tianjin 300071, P. R. China
Fax: +86-22-23502351
E-mail: miaozhiwei@nankai.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201100274.
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Table 1. N-Arylation of imidazole under different conditions.[a]
Entry
Ligand (mol-%)
Copper salt (mol-%)
Base
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
L1 (10)
L2 (10)
L3 (10)
L4 (10)
L5 (10)
L6 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (10)
L5 (20)
L5 (10)
L5 (5)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuSO4 (10)
CuBr (10)
Cu2O (10)
CuAc (10)
CuI (10)
CuI (10)
CuI (10)
CuI (20)
CuI (5)
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
K3PO3
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
DME
CH3CN
toluene
DME
DME
DME
DME
DME
trace
48
56
0
82
73
95
65
49
56
56
42
32
53
28
63
21
48
0
DME
DME
DME
DME
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
–
–
DME
[a] Reaction conditions: unless otherwise noted all the reactions were performed with iodobenzene (1.0 mmol), imidazole (1.0 mmol), Cu
catalyst (0.1 mmol), ligand (0.1 mmol), and Cs2CO3 (2.0 mmol) in the indicated solvent (1.0 mL) at 80 °C under N2 for 20 h. [b] Isolated
yields.
asymmetric reactions.[11] However, this kind of catalytic sys- Cs2CO3 was found to be the most suitable base (Table 1,
tem has not been used in cross-coupling reactions until now. Entries 14–16). The effect of the ratio of the copper salt and
An investigation of solvent effects showed that dimethoxy- the ligand was also studied. The experiments indicated that
ethane (DME) was the best solvent among those screened the catalyst system containing 10 mol-% of CuI and 10 mol-
(dioxane, CH3CN, DME, and toluene; Table 1, Entries 7– % of ligand was the optimal choice (Table 1, Entries 16, 17,
9).
and 7). Reducing the catalyst loading has an influence on
the yield of the reaction. When the catalyst loading was
reduced to 5 mol-%, the coupling reaction gave a yield of
48% (Table 1, Entry 18). A control experiment confirmed
that no product was detected in the absence of ligand
(Table 1, Entry 19). Therefore, the optimal conditions for
the N-arylation process were 10 mol-% of CuI, 10 mol-% of
ligand L5, and 2.0 equiv. of Cs2CO3 in DME.
Based on the above optimization, the scope of aryl halide
substrates was then investigated by using this catalytic sys-
tem. As shown in Table 2, most of the substituted aryl io-
dides and electron-deficient aryl bromides afforded N-aryl-
imidazole products 3a–i in good to excellent yields ranging
from 62 to 94%. However, the arylation of electron-rich
aryl bromides resulted in lower yields (62–79%). Note that
the reaction was highly chemoselective; the reaction be-
tween p-bromoiodobenzene (1f) and imidazole gave 1-(4-
bromophenyl)-1H-imidazole (3f) as the major product
(Table 2, Entry 6).
Figure 1. Ligands L1–L6 for the copper-catalyzed N-arylation of
imidazoles.
With L5 as the optimal ligand, other copper sources were
In an endeavor to expand the scope of the methodology,
examined. The results show that both CuSO4 and CuBr this new catalytic system was applied to benzimidazole and
both gave 56% yields of the desired product, whereas Cu2O pyrrole. The desired amination products from the coupling
and CuAc were less effective in the coupling reaction reactions with the aryl bromides and iodides were obtained
(Table 1, Entries 10–13). As shown in Table 1, with increas- in good to excellent yields (Table 2, Entries 13–19). The re-
ing basicity, K2CO3, K3PO4, and Cs2CO3 showed signifi- sults show that the catalytic system can promote the conver-
cant differences in efficiency in the arylation of imidazole. sion of all of the substrates to the corresponding arylamines
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Cross-Coupling of Aryl Halides with Amines, Phenols, and Thiols
Table 2. Copper-catalyzed cross-coupling of aryl halides with N-aromatic heterocycles and aliphatic amines.[a]
[a] Reaction conditions: 1 (1.0 mmol), 2 (1.0 mmol), Cs2CO3 (2.0 mmol), CuI (10 mol-%), and L5 (10 mol-%) in solvent (2.0 mL) at 80 °C
under N2 for 20 h. [b] Isolated yield.
and that different electronic effects of substituents on the yields (Table 3). We found that iodobenzene bearing elec-
aryl halide are tolerated. Furthermore, the reactions of a tron-releasing groups as well as electron-withdrawing
series of aliphatic N-nucleophiles with aryl halide were per- groups reacted with phenols to give the corresponding di-
formed. As shown in Table 2, all the examined linear and aryl ethers. However, the yields were different with electron-
cyclic aliphatic amines afforded the corresponding N-aryl- rich and electron-deficient phenols. The presence of elec-
ated products in good to excellent yields (Table 2, En- tron-releasing groups such as methyl and methoxy groups
tries 20–27).
at the para position of the phenol led to a decrease in the
yields of the diaryl ethers, whereas an electron-withdrawing
group such as nitro and chloro groups at the para position
of phenol led to an increase in the yields of the desired
Copper-Catalyzed O-Arylation Reactions
The coupling reactions of aryl halides with various sub- products. Under the optimized reaction conditions, bromo-
stituted phenols were carried out under the optimal cataly- benzene also reacted with phenol without increasing the
sis conditions (10 mol-% CuI as copper source, 10 mol-% catalyst loading or the reaction temperature to provide the
L5 as ligand, 2 equiv. of Cs2CO3 as base, DME as solvent) corresponding diaryl ether in good yield (Table 3, En-
and gave the desired aryl ether products in good to excellent try 12).
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Table 3. Copper-catalyzed cross-coupling of aryl halides with substituted phenols.[a]
[a] Reaction conditions: 1 (1.0 mmol), 4 (1.0 mmol), Cs2CO3 (2.0 mmol), CuI (10 mol-%), and L5 (10 mol-%) in solvent (2.0 mL) at 80 °C
under N2 for 20 h. [b] Isolated yield.
Coupling Reactions of Aryl Iodides with Thiols
Conclusions
Finally, we applied our protocol to the CuI-catalyzed S-
We have successfully demonstrated that N,NЈ-dioxide li-
arylation of thiols with various aryl iodides. The optimal
cross-coupling conditions were found to be the same as
those used for the N- and O-arylation reactions, and the
desired aryl thioether products were obtained in good yields
(Table 4). On the basis of the rates and yields of the reac-
tions, our protocol is clearly more effective in the S-aryl-
ation of aryl thiols with aryl iodides than in the N-arylation
of aromatic cyclic secondary amines and the O-arylation of
phenols.
gand L5 can be used as a new, efficient, and versatile ligand
in the copper-catalyzed formation of C–N, C–O, and C–S
bonds. The protocol reported herein is applicable to the
copper-catalyzed cross-coupling reactions of aryl halides
with amines, phenols, and thiols and affords the corre-
sponding desired products in good to excellent yields. In
particular, this catalyst system is versatile and the coupling
reactions promoted by this ligand occurred under mild con-
ditions. Further studies to reduce the catalyst loading and
extend the application of these readily available catalytic
systems to other coupling transformations are on-going as
are mechanistic studies.
Table 4. Copper-catalyzed cross-coupling of aryl halides with sub-
stituted aryl thiols.[a]
Experimental Section
General: All reactions were carried out in resealable test-tubes with
Teflon septa and run under dry nitrogen. Copper(I) iodide (99%)
was purchased from Damao in Tianjin as a red powder. Anhydrous
Cs2CO3 (99.9%) was purchased from Alfa Aesar. Solvents were
dried and distilled prior to use according to standard methods. Un-
less otherwise indicated, all materials were obtained from commer-
cial sources and used as purchased without dehydration. 1H and
13C NMR spectra were recorded in CDCl3 with a Bruker AV 400
(400 MHz) spectrometer. TMS served as the internal standard;
coupling constants J are given in Hz. Mass spectra were recorded
with an LCQ Advantage spectrometer with an ESI resource.
General Procedure for the Preparation of Chiral Ligand L5:[10d]
Et3N (1.55 mL, 15 mmol) and isobutyl carbonochloridate (1.43 g,
11 mmol) were added to a solution of (S)-1-N-Boc-proline-2-carb-
oxylic acid (2.15 g, 10 mmol) in CH2Cl2 (40 mL) at 0 °C whilst
stirring. After 55 min, 2,6-diisopropylphenylamine (2.0 g, 11 mmol)
was added. The reaction mixture was warmed to ambient tempera-
ture and monitored by TLC. The mixture was washed with 1 m
[a] Reaction conditions: 1 (1.0 mmol), 6 (1.0 mmol), Cs2CO3
(2.0 mmol), CuI (10 mol-%), and L5 (10 mol-%) in solvent (2.0 mL)
at 80 °C under N2 for 20 h. [b] Isolated yield.
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Cross-Coupling of Aryl Halides with Amines, Phenols, and Thiols
KHSO4, saturated NaHCO3, brine, dried with anhydrous MgSO4,
and concentrated. TFA (5 mL) was added to the residue in CH2Cl2
(5 mL), and the mixture was stirred until the reaction was finished.
Then the solvent was evaporated, and H2O (10 mL) was added.
The pH value of the mixture was brought into the range of 8–10
by the addition of 1 m NaOH. The aqueous phase was extracted
with CH2Cl2 (5ϫ 20 mL). The combined organic phases were
washed with brine, dried with anhydrous MgSO4, and the solvents
were evaporated in vacuo. The residue was used directly in the next
step. K2CO3 (1.214 g, 8.8 mmol) and 1,3-dibromopropane (204 μL,
2 mmol) were added to a solution of (S)-N-(2,6-diisopropylphenyl)-
proline-2-carboxamide (1.094 g, 4 mmol) in CH3CN (5 mL) whilst
stirring. The mixture was kept at 80 °C and the reaction monitored
by TLC. Then K2CO3 was removed by filtration. The residue was
concentrated and purified by silica gel column chromatography
(EtOAc/n-hexane, 1:1; Rf = 0.3) to give (2S,2ЈS)-1,1Ј-(propane-1,3-
diyl)bis[N-(2,6-diisopropylphenyl)proline-2-carboxamide] (1.060 g,
94% yield). m-CPBA (383 mg, 2.2 mmol) was added to a solution
of (2S,2ЈS)-1,1Ј-(propane-1,3-diyl)bis[N-(2,6-diisopropylphenyl)-
proline-2-carboxamide] (588 mg, 1 mmol) in CH2Cl2 (20 mL) at
0 °C whilst stirring. After the reaction was complete, the mixture
was concentrated and purified by basic aluminium oxide column
chromatography (EtOAc/MeOH, 4:1) to give a white powder of L5
(548 mg, 88% yield).
1-(4-Chlorophenyl)-1H-imidazole (3e): Colorless oil, 169 mg, 95%
yield. H NMR (400 MHz, CDCl3): δ = 7.83 (s, 1 Har), 7.42–7.51
(m, 2 Har), 7.30–7.38 (m, 2 Har), 7.25 (s, 1 Har), 7.21 (s, 1 Har) ppm.
13C NMR (100 MHz, CDCl3): δ = 135.83, 135.49, 133.11, 130.73,
130.01, 122.66, 118.16 ppm. MS (ESI): m/z = 179.20 [M + H]+.
1
1-(4-Bromophenyl)-1H-imidazole (3f): White solid, 198 mg, 89%
1
yield, m.p. 115–117 °C. H NMR (400 MHz, CDCl3): δ = 7.83 (s,
1 Har), 7.56–7.64 (m, 2 Har), 7.23–7.31 (m, 3 Har), 7.21 (s, 1 Har)
ppm. 13C NMR (100 MHz, CDCl3): δ = 136.35, 135.45, 133.00,
130.80, 122.95, 120.90, 118.08 ppm. MS (ESI): m/z = 221.98 [M +
H]+.
1-(4-Phenylphenyl)-1H-imidazole (3g): White solid, 180 mg, 82%
1
yield, m.p. 122–124 °C. H NMR (400 MHz, CDCl3): δ = 7.91 (s,
1 Har), 7.66–7.73 (m, 2 Har), 7.57–7.63 (m, 2 Har), 7.43–7.50 (m, 4
Har), 7.37 (m, 1 Har), 7.33 (s, 1 Har), 7.24 (s, 1 Har) ppm. 13C NMR
(100 MHz, CDCl3): δ = 140.49, 139.71, 136.44, 135.56, 130.53,
128.96, 128.49, 127.79, 127.01, 121.71, 118.20 ppm. MS (ESI): m/z
= 221.27 [M + H]+.
1-(2-Nitrophenyl)-1H-imidazole (3h): Yellow oil, 177 mg, 94% yield.
1H NMR (400 MHz, CDCl3): δ = 7.97–8.06 (m, 2 Har), 7.76–7.80
(m, 1 Har), 7.60–7.69 (m, 1 Har), 7.45–7.52 (m, 1Har), 7.22 (s, 1
Har), 7.08 (s, 1 Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 145.32,
137.25, 133.80, 130.61, 130.41, 129.69, 128.69, 125.39, 120.30 ppm.
MS (ESI): m/z = 190.33 [M + H]+.
General Procedure for the N-, O-, or S-Arylation of Nucleophiles: A
flame-dried Schlenk test-tube with a magnetic stirring bar was
charged with CuI (19.2 mg, 0.1 mmol, 10 mol-%), Cs2CO3 (650 mg,
2.0 mmol), and N,NЈ-dioxide ligand (60 mg, 0.1 mmol, 10 mol-%).
The tube was evacuated and back-filled with nitrogen three times.
Then a solution of halide (1.0 mmol) and nucleophilic reagent
(1.0 mmol) in DME (1 mL) was added through a syringe under a
counter flow of nitrogen at room temperature. The tube was sealed,
and the reaction mixture was heated at 80 °C for 20 h and then
allowed to cool to room temperature. The reaction mixture was
passed directly through Celite. After rinsing with ethyl acetate
(10 mL), the combined filtrates were concentrated by rotary evapo-
ration. The residue was purified by column chromatography on
silica gel by using petroleum ether/ethyl acetate as eluent to give
the desired product.
1-(2-Naphthalen-1-yl)-1H-imidazole (3i): White oil, 153 mg, 79%
yield. H NMR (400 MHz, CDCl3): δ = 7.90–7.96 (m, 2 Har), 7.51
1
(s, 1 Har), 7.46–7.62 (m, 4 Har), 7.40–7.45 (m, 1Har), 7.29 (s, 1 Har),
7.23 (s, 1 Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 138.36,
134.14, 134.02, 129.54, 129.44, 129.24, 128.31, 127.60, 126.97,
125.21, 123.64, 122.29, 121.68 ppm. MS (ESI): m/z = 195.27 [M +
H]+.
1-Phenyl-1H-benzimidazole (3j): Colorless oil, 174 mg, 90% yield.
1H NMR (400 MHz, CDCl3): δ = 8.10 (s, 1 Har), 7.84–7.92 (m, 1
Har), 7.50–7.59 (m, 3 Har), 7.39–7.50 (m, 3 Har), 7.27–7.36 (m, 1
Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.08, 142.32,
136.33, 133.68, 130.08, 128.04, 124.02, 123.72, 122.81, 120.63,
110.50 ppm. MS (ESI): m/z = 195.42 [M + H]+.
1-(4-Methylphenyl)-1H-benzimidazole (3k): Colorless oil, 170 mg,
82% yield. H NMR (400 MHz, CDCl3): δ = 8.07 (s, 1 Har), 7.86–
1-Phenyl-1H-imidazole (3a): Colorless oil, 137 mg, 95% yield. 1H
NMR (400 MHz, CDCl3): δ = 7.85 (s, 1 Har), 7.43–7.52 (m, 2 Har),
7.33–7.42 (m, 3 Har), 7.28 (s, 1 Har), 7.21 (s, 1 Har) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.34, 135.58, 130.46, 129.89, 127.48,
121.46, 118.24 ppm. MS (ESI): m/z = 145.29 [M + H]+.
1
7.88 (m, 1 Har), 7.32–7.51 (m, 7 Har), 2.44 (s, 3 H, CH3) ppm. 13C
NMR (100 MHz, CDCl3): δ = 144.01, 142.41, 138.10, 133.87,
133.78, 130.58, 123.98, 123.58, 122.66, 120.55, 110.50, 21.16 ppm.
MS (ESI): m/z = 209.44 [M + H]+.
1-(4-Tolyl)-1H-imidazole (3b): Colorless oil, 192 mg, 92% yield. 1H
NMR (400 MHz, CDCl3): δ = 7.81 (s, 1 Har), 7.25–7.29 (m, 5 Har),
7.15 (s, 1 Har), 2.40 (s, 3 H, CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 137.43, 135.62, 134.98, 130.35, 130.22, 121.42, 118.35,
20.96 ppm. MS (ESI): m/z = 209.44 [M + H]+.
1-(4-Chlorophenyl)-1H-benzimidazole (3l): Colorless oil, 221 mg,
97% yield. H NMR (400 MHz, CDCl3): δ = 8.08 (s, 1 Har), 7.82–
7.92 (m, 1 Har), 7.52–7.58 (m, 2 Har), 7.42–7.52 (m, 3 Har), 7.32–
7.37 (m, 2 Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.03,
142.02, 134.83, 133.80, 133.49, 130.26, 125.25, 123.92, 123.00,
120.76, 110.20 ppm. MS (ESI): m/z = 229.27 [M + H]+.
1
1-(4-Methoxyphenyl)-1H-imidazole (3c): Colorless oil, 143 mg, 82%
1
yield. H NMR (400 MHz, CDCl3): δ = 7.69 (s, 1 Har), 7.17–7.25
1-(4-Nitrophenyl)-1H-benzimidazole (3m): White solid, 217 mg,
91% yield, m.p. 181–183 °C. 1H NMR (400 MHz, CDCl3): δ =
8.45–8.52 (m, 2 Har), 8.20 (s, 1 Har), 7.56–7.89 (m, 1 Har), 7.71–
7.97 (m, 2 Har), 7.59–7.65 (m, 1 Har), 7.39–7.46 (m, 2 Har) ppm.
13C NMR (100 MHz, CDCl3): δ = 146.54, 144.44, 141.72, 141.58,
132.797, 125.88, 124.62, 123.76, 123.67, 121.23, 110.28 ppm. MS
(ESI): m/z = 240.22 [M + H]+.
(m, 2 Har), 7.06–7.16 (m, 2 Har), 6.85–6.95 (m, 2 Har), 3.75 (s, 3 H,
CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.91, 135.81,
130.63, 129.92, 123.18, 118.77, 114.88, 55.59 ppm. MS (ESI): m/z
= 175.29 [M + H]+.
1-(4-Nitrophenyl)-1H-imidazole (3d): White solid, 180 mg, 95%
yield, m.p. 203–205 °C. 1H NMR (400 MHz, CDCl3): δ = 8.36–
8.44 (m, 2 Har), 7.99 (s, 1 Har), 7.55–7.64 (m, 2 Har), 7.38 (s, 1 Har), 2-(4-Chlorophenyl)-2H-benzotriazole (3n): White solid, 187 mg,
7.28 (s, 1 Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 146.28,
142.00, 135.41, 131.79, 125.81, 121.08, 117.66 ppm. MS (ESI): m/z
= 190.31 [M + H]+.
82% yield, m.p. 121–122 °C. 1H NMR (400 MHz, CDCl3): δ = 8.17
(d, J = 8.4 Hz, 1 Har), 7.74 (dd, J = 13.5, 8.6 Hz, 3 Har), 7.59 (dd,
J = 12.5, 8.3 Hz, 3 Har), 7.46 (t, J = 7.7 Hz, 1 Har) ppm. 13C NMR
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(101 MHz, CDCl3): δ = 134.47, 130.10, 128.52, 124.56, 123.98,
120.54, 110.08, 77.32, 77.00, 76.68 ppm. MS (ESI): m/z = 229.56
[M]+.
1.37–1.37 (m, 2 H, CH2), 0.88 (t, J = 4.0 Hz, 3 H, CH3) ppm. 13C
NMR (100 MHz, CDCl3): δ = 147.07, 129.02, 120.11, 113.74,
43.83, 31.54, 20.27, 13.88 ppm. MS (ESI): m/z = 183.09 [M]+.
Diphenyl Ether (5a): White oil, 166 mg, 98% yield. 1H NMR
(400 MHz, CDCl3): δ = 7.34–7.43 (m, 4 Har), 7.13–7.19 (m, 2 Har),
7.07–7.09 (m, 4 Har) ppm. 13C NMR (100 MHz, CDCl3): δ =
151.27, 129.75, 123.23, 118.91 ppm. MS (ESI): m/z = 170.33 [M]+.
1-(4-Methoxyphenyl)pyrrole (3o): White solid, 108 mg, 63% yield,
m.p. 88–89 °C. H NMR (400 MHz, CDCl3): δ = 7.52–7.57 (m, 2
1
Har), 7.27–7.34 (m, 2 Har), 6.98 (s, 2 Har), 6.32 (s, 2 Har) ppm. 13C
NMR (100 MHz, CDCl3): δ = 138.16, 122.15, 119.66, 116.31,
114.57, 109.80, 55.53, 55.28 ppm. MS (ESI): m/z = 174.22 [M +
H]+.
4-Methylphenyl Phenyl Ether (5b): White oil, 134 mg, 73% yield.
1H NMR (400 MHz, CDCl3): δ = 8.04 (s, 1 Har), 7.90–7.84 (m, 1
Har), 7.48–7.43 (m, 1 Har), 7.42–7.37 (m, 2 Har), 7.34–7.29 (m, 2
Har), 7.08–7.03 (m, 2 Har), 3.88 (s, 3 H, CH3) ppm. 13C NMR
(100 MHz, CDCl3): δ = 159.27, 143.80, 142.54, 134.19, 129.10,
125.68, 123.49, 122.55, 120.47, 115.07, 110.32, 55.62 ppm. MS
(ESI): m/z = 184.16 [M]+.
1-(4-Chlorophenyl)pyrrole (3p): White solid, 132 mg, 75% yield,
1
m.p. 88–89 °C. H NMR (400 MHz, CDCl3): δ = 7.35–7.42 (m, 2
Har), 7.28–7.35 (m, 2 Har), 7.04 (s, 2 Har), 6.35 (s, 2 Har) ppm. 13C
NMR (100 MHz, CDCl3): δ = 139.23, 130.98, 129.59, 121.57,
119.24, 110.78 ppm. MS (ESI): m/z = 177.23 [M]+.
N-(4-Methylphenyl)benzylamine (3q): White oil, 136 mg, 69% yield.
1H NMR (400 MHz, CDCl3): δ = 7.21–7.31 (m, 4 Har), 7.14–7.20
(m, 1 Har), 6.84–6.95 (m, 2 Har), 6.43–6.50 (m, 2 Har), 4.20 (s, 2 H,
CH2), 2.14 (s, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ =
144.86, 138.60, 128.69, 127.54, 126.44, 126.09, 125.66, 47.55,
19.36 ppm. MS (ESI): m/z = 199.33 [M + H]+.
4-Methoxyphenyl 4-Methylphenyl Ether (5c): White oil, 173 mg,
81% yield. H NMR (400 MHz, CDCl3): δ = 7.05–7.13 (m, 2 Har),
6.91–6.99 (m, 2 Har), 6.81–6.90 (m, 4 Har), 3.79 (s, 3 H, CH3), 2.30
(s, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.05,
155.57, 150.67, 131.98, 130.07, 120.32, 117.75, 114.73, 55.61,
20.61 ppm. MS (ESI): m/z = 214.07 [M]+.
1
N-(4-Methoxyphenyl)benzylamine (3r): White oil, 134 mg, 63%
yield. 1H NMR (400 MHz, CDCl3): δ = 7.30–7.41 (m, 4 Har), 7.21–
7.29 (m, 1 Har), 6.73–6.80 (m, 2 Har), 6.56–6.63 (m, 2 Har), 4.26 (s,
2 H, CH2), 3.72 (s, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3):
δ = 152.19, 142.48, 139.722, 128.63, 127.58, 127.21, 114.92, 114.12,
55.83, 49.25 ppm. MS (ESI): m/z = 214.32 [M + H]+.
4-Methylphenyl 4-Nitrophenyl Ether (5d): White solid, 222 mg, 97%
yield, m.p. 111–112 °C. 1H NMR (400 MHz, CDCl3): δ = 8.15–
8.21 (m, 2 Har), 7.20–7.25 (m, 2 Har), 6.95–7.00 (m, 4 Har), 2.37 (s,
3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 163.78, 152.23,
142.34, 135.23, 130.79, 125.90, 120.48, 116.69, 20.85 ppm. MS
(ESI): m/z = 229.12 [M]+.
N-(4-Nitrophenyl)benzylamine (3s): White oil, 190 mg, 91% yield.
1H NMR (400 MHz, CDCl3): δ = 7.76 (s, 1 Har), 7.33 (s, 2 Har),
7.16–7.24 (m, 2 Har), 6.96–7.03 (m, 4 Har), 3.85 (s, 2 H, CH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 158.92, 135.90, 130.74, 130.10,
123.24, 118.80, 114.89, 55.63 ppm. MS (ESI): m/z = 209.20 [M +
H]+.
4-Chlorophenyl 4-Methylphenyl Ether (5e): White oil, 194 mg, 89%
yield. 1H NMR (400 MHz, CDCl3): δ = 7.15–7.21 (m, 2 Har), 7.03–
7.09 (m, 2 Har), 6.75–6.85 (m, 4 Har), 2.26 (s, 3 H, CH3) ppm. 13C
NMR (100 MHz, CDCl3): δ = 155.46, 153.26, 132.33, 129.32,
128.55, 126.65, 118.41, 118.10, 19.69 ppm. MS (ESI): m/z = 218.09
[M]+.
N-(4-Chlorophenyl)benzylamine (3t): White oil, 184 mg, 85% yield.
1H NMR (400 MHz, CDCl3): δ = 7.31–7.35 (m, 4 Har), 7.24–7.30
(m, 1 Har), 7.05–7.13 (m, 2 Har), 6.45–6.55 (m, 2 Har), 4.27 (s, 2 H,
CH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 146.68, 138.97,
129.11, 128.75, 127.45, 127.42, 122.09, 48.34 ppm. MS (ESI): m/z
= 218.07 [M + H]+.
4-Chlorophenyl Phenyl Ether (5f): White oil, 142 mg, 70% yield. 1H
NMR (400 MHz, CDCl3): δ = 7.26–7.36 (m, 4 Har), 7.08–7.14 (m,
1 Har), 7.10–7.13 (m, 1 Har), 6.92–7.00 (m, 4 Har) ppm. 13C NMR
(100 MHz, CDCl3): δ = 156.83, 155.91, 129.85, 129.68, 128.15,
123.60, 120.00, 118.90 ppm. MS (ESI): m/z = 204.08 [M]+.
4-tert-Butylphenyl 3-Methylphenyl Ether (5g): White oil, 194 mg,
81% yield. H NMR (400 MHz, CDCl3): δ = 7.19–7.28 (m, 2 Har),
4-Chloro-N-cyclohexylaniline (3u): Yellow oil, 163 mg, 78% yield.
1H NMR (400 MHz, CDCl3): δ = 7.11 (d, J = 7.2 Hz, 2 Har), 6.52
(d, J = 7.3 Hz, 2 Har), 3.55 (s, 1 H, NH), 3.20 (s, 1 H, CH), 2.06
(d, J = 12.3 Hz, 2 H, CH2), 1.78 (d, J = 10.8 Hz, 2 H, CH2), 1.39
(dd, J = 24.5, 12.5 Hz, 2 H, CH2), 1.09–1.31 (m, 4 H, 2 CH2) ppm.
13C NMR (101 MHz, CDCl3): δ = 146.63, 129.75, 121.93, 114.86,
52.56, 34.01, 26.57, 25.65 ppm. MS (ESI): m/z = 209.45 [M]+.
1
7.06–7.15 (m, 1 Har), 6.77–6.89 (m, 3 Har), 6.67–6.77 (m, 2 Har),
2.23 (s, 3 H, CH3), 1.23 (s, 9 H, 3 CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 156.42, 153.74, 144.872, 138.76, 128.30, 125.43,
122.71, 118.27, 117.31, 114.59, 33.23, 30.46, 20.35 ppm. MS (ESI):
m/z = 240.10 [M]+.
3,5-Bis(trifluoromethyl)phenyl 4-tert-Butylphenyl Ether (5h): White
oil, 282 mg, 78% yield. 1H NMR (400 MHz, CDCl3): δ = 7.53–
7.57 (m, 1 Har), 7.41–7.45 (m, 2 Har), 7.36–7.40 (m, 2 Har), 6.91–
7.01 (m, 2 Har), 1.35 (s, 9 H, 3 CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 159.05, 152.46, 148.23, 133.58, 133.24, 132.91, 132.57,
127.25, 124.36, 121.65, 119.36, 117.68, 117.65, 115.94, 115.90,
115.86, 34.51, 31.41 ppm. MS (ESI): m/z = 362.01 [M]+.
4-(4-Chlorophenyl)morpholine (3v): White oil, 134 mg, 68% yield.
1H NMR (400 MHz, CDCl3): δ = 7.24 (d, J = 7.8 Hz, 2 Har), 6.85
(d, J = 7.8 Hz, 2 Har), 3.88 (d, J = 2.0 Hz, 4 H, 2 CH2), 3.14 (d, J
= 1.9 Hz, 4 H, 2 CH2) ppm. 13C NMR (101 MHz, CDCl3): δ =
150.61, 129.74, 125.59, 117.60, 78.05, 77.74, 77.42, 67.49,
50.03 ppm. MS (ESI): m/z = 197.06 [M]+.
1-(4-Chlorophenyl)piperidine (3w): Yellow oil, 140 mg, 72% yield.
1H NMR (400 MHz, CDCl3): δ = 7.22 (t, J = 8.9 Hz, 2 Har), 6.88
(d, J = 7.9 Hz, 2 Har), 3.13–3.15 (m, 4 H, 2 CH2), 1.72 (s, 4 H, 2
CH2), 1.60 (d, J = 5.2 Hz, 2 H, CH2) ppm. 13C NMR (101 MHz,
Bis(4-chlorophenyl) Ether (5i): White oil, 179 mg, 75% yield. 1H
NMR (400 MHz, CDCl3): δ = 7.24–7.32 (m, 4 Har), 6.87–6.95 (m,
4 Har) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.57, 129.90,
128.68, 120.13 ppm. MS (ESI): m/z = 240.01 [M]+.
CDCl3):
δ = 130.57, 129.55, 120.81, 118.38, 51.39, 26.40,
24.85 ppm. MS (ESI): m/z = 195.08 [M]+.
4-tert-Butylphenyl 4-Methylphenyl Ether (5j): White oil, 175 mg,
1
N-Butyl-4-chloroaniline (3x): White oil, 113 mg, 62% yield. 1H
73% yield. H NMR (400 MHz, CDCl3): δ = 7.30 (s, 2 Har), 7.08–
NMR (400 MHz, CDCl3): δ = 7.02–7.43 (m, 2 Har), 6.42 (d, J = 7.14 (m, 2 Har), 6.88–6.93 (m, 4 Har), 2.31 (s, 3 H, CH3), 1.32 (s, 9
4.0 Hz, 2 Har), 2.97–3.01 (m, 2 H, CH2), 1.49–1.53 (m, 2 H, CH2),
H, 3 CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.35, 155.08,
3358
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 3353–3360

Cross-Coupling of Aryl Halides with Amines, Phenols, and Thiols
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J. Org. Chem. 2004, 69, 5578–5587; b) D. van Allen, D. Venkat-
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145.69, 132.62, 130.22, 126.51, 118.95, 118.65, 117.95, 115.96,
34.32, 31.58, 20.77 ppm. MS (ESI): m/z = 240.14 [M]+.
4-tert-Butylphenyl 4-Chlorophenyl Ether (5k): White oil, 221 mg,
1
85% yield. H NMR (400 MHz, CDCl3): δ = 7.14–7.25 (m, 4 Har),
6.78–6.84 (m, 4 Har), 1.21 (s, 9 H, 3 CH3) ppm. 13C NMR
(100 MHz, CDCl3): δ = 155.50, 153.50, 145.76, 128.81, 127.02,
125.88, 118.93, 117.73, 33.54, 30.68 ppm. MS (ESI): m/z = 260.22
[M]+.
[3]
1
Diphenyl Sulfide (7a): Colorless oil, 176 mg, 95% yield. H NMR
(400 MHz, CDCl3): δ = 7.34–7.42 (m, 10 Har) ppm. 13C NMR
(100 MHz, CDCl3): δ = 136.55, 131.79, 129.95, 127.80 ppm. MS
(ESI): m/z = 186.22 [M]+.
4-Methylphenyl Phenyl Sulfide (7b): White oil, 180 mg, 90% yield.
1H NMR (400 MHz, CDCl3): δ = 7.13–7.30 (m, 9 Har), 2.35 (s, 3
H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.63, 137.14,
132.30, 130.08, 129.78, 129.06, 126.42, 31.62 ppm. MS (ESI): m/z
= 200.07 [M]+.
[4]
[5]
3-Chlorophenyl Phenyl Sulfide (7c): White oil, 200 mg, 91% yield.
1H NMR (400 MHz, CDCl3): δ = 6.95–7.49 (m, 9 Har) ppm. 13C
NMR (100 MHz, CDCl3): δ = 133.29, 130.14, 129.79, 129.64,
129.12, 128.37, 127.54, 127.30, 127.26 ppm. MS (ESI): m/z =
221.08 [M]+.
4-Chlorophenyl Phenyl Sulfide (7d): White oil, 195 mg, 89% yield.
1H NMR (400 MHz, CDCl3): δ = 7.23–7.31 (m, 9 Har) ppm. 13C
NMR (100 MHz, CDCl3): δ = 135.18, 134.70, 133.04, 132.07,
131.37, 129.37, 129.12, 129.49 ppm. MS (ESI): m/z = 221.08 [M]+.
3-Methylphenyl Phenyl Sulfide (7e): White oil, 150 mg, 75% yield.
1H NMR (400 MHz, CDCl3): δ = 7.18–7.50 (m, 9 Har), 2.35 (s, 3
H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 131.89, 130.79,
129.61, 128.37, 128.06, 127.53, 127.19, 126.88, 21.33 ppm. MS
(ESI): m/z = 200.07 [M]+.
[6]
[7]
[8]
4-Chlorophenyl 4-Methylphenyl Sulfide (7f): White solid, m.p.
1
208 mg, 89% yield, 110–112 °C. H NMR (400 MHz, CDCl3): δ =
7.17–7.33 (m, 8 Har), 2.38 (s, 3 H, CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 138.77, 136.66, 133.21, 132.99, 131.50, 131.37, 130.92,
129.85, 21.87 ppm. MS (ESI): m/z = 234.04 [M]+.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, product isolation, and 1H and 13C
NMR spectra of the prepared compounds.
Acknowledgments
We thank the National Natural Science Foundation of China
(21072102), the Committee of Science and Technology of Tianjin
(11JCYBJC04200), and the State Key Laboratory of Elemento-
Organic Chemistry at Nankai University for financial support.
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3359

H. Yang, C. Xi, Z. Miao, R. Chen
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Received: February 27, 2011
Published Online: May 6, 2011
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