One-pot two-step synthesis of: N -arylcarbazole-based skeleton

Article abstract of DOI:10.1039/c5ra26698j

A highly site-selective, one-pot, sequential C-N and C-C bond forming process was developed, affording a carbazole-based skeleton that contains biphenyl and diarylacetylene cores. The success of this process is attributed to the use of fluorinated iodoarenes as the starting material, the fluorine group of which preferentially reacts with carbazole. The subsequent coupling of the intermediate iodinated N-arylcarbazole with arylboronic acid or arylacetylene produced the desired products. The intermediate underwent a Pd-catalyzed Ullmann coupling with excess fluorinated iodoarenes in the absence of arylboronic acid or arylacetylene, resulting in Ullmann coupling products in a one-pot process.

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One-pot two-step synthesis of N-arylcarbazole-based skeleton
Sheng Tao, Ning Liu,* and Bin Dai*
Received 00th January 20xx,
Accepted 00th January 20xx
A highly site-selective, one-pot, sequential C–N and C–C bond forming process was developed, affording carbazole-based
skeleton that contained biphenyl and diarylacetylene cores. The success of this process is attributed to the use of
fluorinated iodoarenes as starting material, the fluorine group of which preferentially reacts with carbazole. The
subsequent coupling of the intermediate iodinated N-arylcarbazole with arylboronic acid or arylacetylene produced
desired products. The intermediate underwent Pd-catalyzed Ullmann coupling with excess fluorinated iodoarenes in the
DOI: 10.1039/x0xx00000x
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absence of arylboronic acid or arylacetylene, resulting in Ullmann coupling products in
a one-pot process.
coupling between 9-(4-iodophenyl)-9H-carbazole and 4-fluoro-
iodobenzene smoothly proceeded and then resulted in
products.
Introduction
Carbazole-based skeleton that contains biphenyl and
diarylacetylene cores is widely applied in dye-sensitized solar
cells1 and organic light-emitting diodes,2 and as key
component in the construction of natural products.3
Previous methods (two-pot)
(2) arylboronic acid
N
Ar
Pd, ligand
Carbazole-based skeleton compounds are synthesized via two-
pot synthetic approaches.4 N-Arylated carbazoles are prepared
through copper-catalyzed C–N forming reaction between
carbazoles and dihalobenzene. After purification, the
intermediate undergoes cross-coupling with arylboronic acid5
or arylacetylene6 in the presence of palladium as catalyst. One-
Br
Br
Cu, base
Suzuki coupling (Ref. 5)
+
N
Br
H
N
(2) aryl acetylene
Pd, ligand
N
Ar
pot strategy is
a useful technique in synthetic organic
Sonogashira coupling (Ref. 6)
chemistry, because it can minimizes solvent use, time, and the
number of purification steps compared with individual multi-
step syntheses.7 We attempted to develop a one-pot method
without purification step to prepare carbazole-based skeleton
compounds. We have recently developed a copper-catalysed
method for N-arylation of carbazole.8 The study showed that
halogenated fluorobenzenes undergo a highly site-selective
coupling at the fluoride group with carbazole through
nucleophilic substitution reaction in the metal-free condition.
We infer that the metal-free condition eliminates the
interference of metal for the succeeding transformation, and
the tolerated halides provide an opportunity to enhance the N-
arylated carbazole compounds further and convert them into
useful compounds. In this paper, fluorinated iodobenzenes
underwent sequential N-arylation and palladium-catalysed
cross-coupling to achieve desired products with good yields. In
the absence of arylboronic acids or arylacetylene, the Ullmann
This work (one-pot two-step)
high selectivity
• good yield
• broad substrate scope
easy operation
•
N
Ar
•
arylboronic acid
Suzuki coupling
F
I
Ullmann coupling
Cs2CO3, DMA
150 oC, 24 h
+
N
I
N
F
Without add ing
any substrates
H
N
arylacetylene
Sonogashira coupling
N
Ar
Figure 1 Methods for synthesis of carbazole-based skeleton.
Results and Discussion
One-pot two-step N-arylation and Pd-catalysed Suzuki coupling
among 4-fluoro-iodobenzene, carbazole, and phenylboronic
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acid was selected as the model reaction to optimize the produced best yields (Table 1, entry 8). The yield decreased
reaction conditions. The reaction conditions, including Pd upon switching to DMF (N,N-dimethylformamide), NMP (N-
sources, solvents, and molar ratios of substrates, were methyl-2-pyrrolidone), or DMSO (dimethyl sulfoxide) (Table 1,
evaluated.
entries 9, 10, and 11). Pd-catalysed cross-coupling is often
The effect of molar ratio of substrates on the coupling of 4- affected by Pd source. Therefore, we evaluated different Pd
fluoro-iodobenzene with carbazole was initially examined. sources. The experimental results showed that PdCl2 was more
Molar ratio is a crucial factor for product yield. A 1.0:0.5:1.0 catalytically active than the other Pd sources (Table 1, entry
molar ratio of 4-fluoro-iodobenzene, carbazole, and 12).
phenylboronic acid was the optimal reaction condition for the The effect of temperature for the N-arylation was investigated.
one-pot two-step method (Table 1, entry 8).
The reaction rate remarkably accelerated when the increasing
temperature from 130 C to 150 C (Table 1, entries 15, and
12). Upon further increase of the reaction temperature to 170
C, the isolated yield slightly decreased to 83% (Table 1, entry
°
°
Table 1 One-pot substitution-Suzuki coupling process: optimization
°
of reaction conditiona
16). Nuclear magnetic resonance analysis showed that too
high reaction temperature was likely to form disubstituted
side-products due to the selectivity decrease of 4-fluoro-
iodobenzene.
The effect of temperature for the Suzuki coupling was also
investigated. The temperature has an evident promoting effect
Entry Solvent
Molar ratio (1a:1b:1c)
0.5:0.5:0.5
0.5:0.75:0.5
0.5:1.0:0.5
0.5:1.0:1.0
1.0:0.5:0.5
2.0:0.5:0.5
1.0:0.5:2.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:.0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:.0.5:1.0
1.0:.0.5:1.0
1.0:.0.5:1.0
1.0:.0.5:1.0
1.0:.0.5:1.0
Palladium
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
Yield (%)
22
on the reaction rate when from 90
entries 17, 18, and 19). Upon further increase of the reaction
temperature to 130 C, but has no evident change in yield
(Table 1, entry 12). Therefore, 120 C was selected as the
°C to 120 °C (Table 1,
1
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMF
DMSO
NMP
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
°
2
42
°
optimised reaction temperature used in subsequent studies.
The scope and limitations for the Suzuki coupling of
arylboronic acids were initially examined (Table 2).
3
38
4
31
The reactivity of arylboronic acids was tested under optimised
reaction conditions. The desired products were obtained in
good-to-excellent yields (Table 2, 2a-h). The electronic effect
of para-substituents that bear the aromatic ring of boronic
acids was observed. Arylboronic acids that contained electron-
donating and electron-neutral groups such as 4-H, 4-Me, and
4-nPr, smoothly reacted with intermediates generated from N-
arylation, resulting in high-yield products (Table 2, 2a-c).
However, the arylboronic acids that contained electron-
withdrawing group were less reactive in the developed system
and produced moderate product yields (Table 2, 2d-f). The
electronic effect of meta-substituted arylboronic acids was not
5
73
6
63
7
79
8
83
9
51
10
11
12
13
14
15b
16c
17d
18e
19f
a
72
49
88
evident
in
the
developed
one-pot
system.
3-
Pd(OH)2
Pd/C
81
Methylphenylboronic acid successfully reacted with 9-(4-
iodophenyl)-9H-carbazole to provide good results (Table 2, 2g).
The steric hindrance effect of ortho-substituted arylboronic
acids presented a certain influence on the reaction rate. 2-
Methylphenylboronic acid showed considerably slower
conversion and obtained moderate yield (Table 2, 2h).
74
PdCl2
62
PdCl2
83
PdCl2
89
The Suzuki coupling was not affected by the electronic nature
and steric hindrance effects of fluorinated iodobenzenes. Thus,
3-iodo- or 2-iodo-substituted carbazolylbenzene smoothly
underwent coupling with arylboronic acids and resulted in
moderate to good yield products (Table 2, 2i-l).
PdCl2
80
PdCl2
52
Reaction conditions: (1) 4-fluoro-iodobenzene, carbazole, Cs2CO3 (1.0
mmol) in solvent (1 mL) under air, 150 °C, 24 h. 130 °C. 170 °C. (2)
phenylboronic acid, palladium source (5 mol%), PPh3 (10 mol%), were added
without purification step, 130 °C, 6 h. Isolated yield. 120 °C. 110 °C. 90
°C.
b
c
The scope of coupling for carbazoles was also investigated
under optimised reaction conditions. The electronic effect of
carbazoles was not evident. Thus, 3,6-ditert-butyl 3,6-dibromo,
and 2,7-dibromo group substituted carbazoles smoothly
underwent coupling and produced good yields (Table 2, 2m-p).
d
e
f
The effect of different solvents was also determined. The
reaction carried out in DMA (N,N-dimethylacetamide)
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Table 2 One-pot substitution-Suzuki coupling processa
One-pot two-step process through N-arylation and Pd-
catalyzed Sonogashira coupling among 4-fluoro-iodobenzene,
carbazole, and phenylacetylene was selected as the model
reaction to optimize the reaction conditions. In this model,
different reaction conditions, including Pd sources, solvents,
and molar ratios of substrates, were evaluated. A 1.0:0.5:1.0
molar ratio of 4-fluoro-iodobenzene, carbazole, and
phenylacetylene was the optimal reaction condition for the
one-pot method (Table 3, entry 5).
To probe the efficiency of CuI and Et3N, we designed control
experiments by conducting the reaction in the absence of CuI
and Et3N, respectively. The results indicated that the CuI can
efficiently promote the coupling reaction from 75% to 93% of
the product yield (Table 3, entry 5 vs. 11). Et3N is crucial for
the reaction. The reaction was difficult to proceed in the
absence of Et3N, and only 13% product yield was obtained
(Table 3, entry 12).
Table 3. One-pot substitution-Sonogashira coupling process:
optimization of reaction conditiona
Entry Solvent
Molar ratio (1a:1b:1d)
0.5:0.5:1.0
0.5:0.75:1.0
0.5:1.0:1.0
0.5:2.0:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
1.0:0.5:1.0
Palladium
PdCl2
Yield (%)
67
1
DMA
DMA
DMA
DMA
DMA
DMSO
DMF
NMP
DMA
DMA
DMA
DMA
DMA
DMA
DMA
2
PdCl2
52
3
PdCl2
81
4
PdCl2
41
5
PdCl2
93
6
PdCl2
84
7
PdCl2
46
8
Pd(OAc)2
Pd(OH)2
Pd/C
78
9
68
a
10
11b
12c
13d
14e
15f
a
63
Reaction conditions: (1) fluorinated iodobenzenes (1.0 mmol), carbazoles
(0.5 mmol), Cs2CO3 (1.0 mmol) in DMA (1 mL) under air, 150 °C, 24 h. (2)
phenylboronic acid (1.0 mmol), PdCl2 (5 mol%), PPh3 (10 mol%), were added
without purification step, 120 °C, 6 h. Isolated yield. b 130 °C.
PdCl2
75
PdCl2
13
Arylboronic acids containing sensitive groups such as 4-OH, 4-
CHO, 4-COOEt, 4-CN, and 4-OMe, were evaluated in the
developed catalytic system. The results showed that no
desired products were obtained. Arylboronic acids bearing 4-
OH, 4-CHO, 4-COOEt, and 4-CN, have not participated in the
reaction, but a sequential N-arylation and Ullmann coupling
occurred between 4-fluoro-iodobenzene and carbazole (Table
2). 4-Methoxyphenylboronic acid preferentially reacted with 4-
fluoro-iodobenzene to generate 4-fluoro-4'-methoxy-1,1'-
biphenyl compound instead of attacking on the intermediate
from the N-arylation between 4-fluoro-iodobenzene and
carbazole (Table 2, 2q).
PdCl2
89
PdCl2
83
PdCl2
70
Reaction conditions: (1) 4-fluoro-iodobenzene, carbazole, Cs2CO3 (1.0
mmol) in solvent (1 mL) under air, 150 °C, 24 h. (2) phenylacetylene (1.0
mmol), palladium source (5 mol%), CuI (2.5 mol%), PPh3 (10 mol%), Et3N (1
b
mmol), were added without purification step, 130 °C, 6 h. Isolated yield.
Without CuI. c Without Et3N. d 120 °C. e 110 °C. f 90 °C.
The effect of temperature for the Sonogashira coupling was
investigated (Table 3, entries 5, 13, 14, and 15). 130 °C was
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selected as the optimised reaction temperature for However, the arylacetylenes bearing electron-withdrawing
Sonogashira coupling (Table 3, entry 5). group were less reactive in the developed one-pot system and
The scope and limitations for the Sonogashira coupling of resulted in moderate product yields (Table 4, 3d and 3e). The
arylacetylenes were examined. The reactivity of arylacetylenes reactivity of arylacetylenes decreased when their groups bear
was tested under optimised reaction conditions, and the at the meta-position (Table 4, 3f and 3g). Steric hindrance
desired products were obtained in good to excellent yields effect of ortho-substituted arylacetylenes was not observed in
(Table 4).
the developed system (Table 4, 3h).
The scope of one-pot method for carbazoles was also
investigated under the optimised reaction conditions. The
electronic effect of carbazoles was significantly evident.
Carbazoles bearing 3,6-ditert-butyl group exhibited higher
reactivity than those bearing 3,6-dibromo and 2,7-dibromo
groups (Table 4, 3i vs. 3j-l).
Table 4. One-pot substitution-Sonogashira coupling processa
The optimised reaction conditions were also applied in the
coupling of alicyclic and aliphatic alkynes. The reactivity of
alicyclic alkynes was evidently higher than aliphatic alkynes
(Table 4, 3m-o vs. 3p). Alicyclic alkynes were successfully
converted to the desired products with excellent yields (Table
4, 3m-o). However, aliphatic alkynes showed considerably
slower conversion and resulted in moderate product yield in
the same reaction condition (Table 4, 3p).
Arylacetylenes containing sensitive groups such as 3-OH, 3-NH2,
4-COOMe, 4-CH2CN, and 4-OMe, were evaluated in the
developed catalytic system. 3-Ethynylphenol and 3-
ethynylaniline have not participated in the reaction, but
coupling product through sequential N-arylation and Ullmann
coupling was obtained (Table 4). Arylacetylenes bearing 4-
COOMe, 4-CH2CN, and 4-OMe, preferentially reacted with 4-
fluoro-iodobenzene instead of attacking on the intermediate
from the N-arylation between 4-fluoro-iodobenzene and
carbazole (Table 4, 3q-s).
In view of the unexpected results in Table 2, and 4, arylboronic
acid or arylacetylene was eliminated from the reaction system.
The results showed that the reaction process was not
terminated in the N-arylation of carbazole in the presence of
palladium catalyst. Instead, the process continued to react
with fluorinated iodobenzenes through the Ullmann coupling
and yielded products.
The reaction conditions of the one-pot two-step method for N-
arylation and Ullmann coupling were evaluated (Table 5). A
1.5:0.5 molar ratio of 4-fluoro-iodobenzene and carbazole was
the optimal reaction conditions for the one-pot two-step
method in DMA in the presence of PdCl2 as catalyst (Table 5,
entry 3). Palladium catalyst was crucial for the Ullmann
coupling between 9-(4-iodophenyl)-9H-carbazole and 4-fluoro-
iodobenzene.
To investigate the efficiency of CuI, PdCl2, and Et3N, we
designed three control experiments (Table 5, entries 11-13).
The results showed that CuI inhibited Ullmann coupling
reaction and homo-coupling of 4-fluoro-iodobenzene
increased (Table 5, entry 11). Et3N can efficiently promote the
coupling reaction (Table 5, entry 12). The coupling reaction
was difficult to start in the absence of Pd catalyst (Table 5,
entry 13).
a
Reaction conditions: (1) fluorinated iodobenzenes (1.0 mmol),
carbazoles (0.5 mmol), Cs2CO3 (1.0 mmol) in DMA (1 mL) under air,
150 °C, 24 h. (2) arylacetylene (1.0 mmol), PdCl2 (5 mol%), CuI (2.5
mol%), PPh3 (10 mol%), Et3N (1 mmol), were added without
purification step, 130 °C, 6 h. Isolated yield.
The electronic effect of para-substituents bearing the aromatic
ring of arylacetylenes was evident. Arylacetylenes containing
electron-donating and electron-neutral groups were highly
reactive and resulted in excellent yields (Table 4, 3a-c).
The effect of temperature for the Ullman coupling was
investigated (Table 5, entries 3, 14, 15, and 16). The results
showed that the temperature served a crucial function in the
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Ullman coupling. The higher reaction temperature is necessary
to activate the intermediate from N-arylation between
Table 6. One-pot substitution-Ullmann coupling processa
fluorinated iodobenzenes and carbazole, so 130
°C was
selected as the optimised reaction temperature (Table 5, entry
3).
R1
[1] carbazoles
DMA, Cs2CO3, 150 o
F
I
C
F
N
[2] PdCl2, PPh3, Et3N
Table 5. One-pot substitution-Ullmann coupling process:
R2
optimization of reaction conditiona
F
N
F
N
Entry
1
Solvent
DMA
DMA
DMA
DMA
DMSO
DMF
Molar ratio (1a:1b)
0.75:0.5
1.0:0.5
Palladium
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
Pd(OAc)2
Pd(OH)2
Pd/C
Yield (%)
47
2d, 64%
4a, 56%
tBu
F
2
68
N
F
3
1.5:0.5
83
N
4
2.0:0.5
85
tBu
4b, 19%
4c, 28%
5
1.5:0.5
72
Br
Br
6
1.5:0.5
58
N
F
7
NMP
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
1.5:0.5
64
N
F
8
1.5:0.5
77
4d,43%
Br
4e, 45%
9
1.5:0.5
69
Br
Br
10
11b
12c
13d
14e
15f
16g
a
1.5:0.5
65
1.5:0.5
PdCl2
PdCl2
no
73
N
F
N
F
1.5:0.5
53
4g, 48%
O2N
1.5:0.5
0
4f, 39%
1.5:0.5
PdCl2
PdCl2
PdCl2
66
a Reaction conditions: (1) fluorinated iodobenzenes (1.0 mmol), carbazoles
(0.5 mmol), Cs2CO3 (1.0 mmol) in DMA (1 mL) under air, 150 °C, 24 h. (2)
PdCl2 (5 mol%), PPh3 (10 mol%), and Et3N (1.0 mmol), were added
without purification step, 130 °C, 6 h. Isolated yield.
1.5:0.5
57
1.5:0.5
35
Reaction conditions: (1) 4-fluoro-iodobenzene, carbazole, Cs2CO3 (1.0
mmol) in solvent (1 mL) under air, 150 °C, 24 h. (2) phenylacetylene (1.0
mmol), palladium source (5 mol%), PPh3 (10 mol%), Et3N (1 mmol), were
added without purification step, 130 °C, 6 h. Isolated yield. b Adding CuI (2.5
mol%). c Without Et3N. d Without PdCl2. e 120 °C. f 110 °C. g 90 °C.
To simplify the operating procedures, we simultaneously
conducted N-arylation and Pd-catalysed cross coupling
reactions in one-pot (Figure 2). Interestingly, the one-pot
method for N-arylation and Pd-catalysed Sonogashira coupling
showed a slight decrease in yield and achieve high conversion
(Figure 2). However, N-arylation and Pd-catalysed Suzuki
coupling in one-pot is difficult to perform simultaneously
(Figure 2). In the presence of Pd-catalyst, 4-fluoro-
iodobenzene preferred to react with phenylboronic acid or
undergo homo-couple to afford products 5a and 5b. The one-
pot method for N-arylation and Pd-catalysed Ullmann coupling
showed evident decrease in yield and achieved high
conversion (Figure 2). The product analysis revealed that the
The scope and limitations for N-arylation and Pd-catalyzed
Ullmann coupling were evaluated (Table 6). The electronic
effect of the fluorine group bearing the iodobenzene ring was
not observed. The iodobenzene with fluorine substitution at
the para or meta position to the aromatic ring showed similar
reactivity and produced moderate yield (Table 6, 2d and 4a).
The steric hindrance effect of fluorinated iodobenze was
evident and only 19% desired product yield was obtained
(Table 6, 4b). The electronic effect of carbazole was also
evident for Ullmann coupling. The carbazole with electronic-
withdrawing group at the para position to the aromatic ring
showed higher reactivity than that with electronic-donating
group (Table 6, 4c vs. 4d-g).
Pd-catalyst activated the C
–I bond of fluorinated iodobenzene
and lead to decrease reaction selectivity.
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General procedure for substitution-Suzuki coupling process. A
mixture of 4-fluoro-iodobenzene (1.0 mmol), carbazoles (0.5 mmol),
Cs2CO3 (0.05 mmol) was added to a glass vial in solvent (1 mL)
under air atmosphere. The reaction mixture was heated to 150 °C
for 24 h. The reaction mixture was cooled to room temperature. To
this mixture was added arylboronic acid (1.0 mmol), palladium
sources (0.025 mmol), and PPh3 (0.05 mmol), and the mixture was
heated to 130 °C for 6 h. The reaction mixture was added to brine
(15 mL) and extracted three times with dichloromethane (3×15 mL).
The solvent was concentrated under vacuum and the product was
isolated by short chromatography on a silica gel (200–300 mesh)
column.
mixture
F
F
F
+
5a, NMR yield 34%
5b, NMR yield 42%
Suzuki coupling
PdCl2, PPh3, Cs2CO3,
Et3N, DMA, 24 h, 150 o
N
F
Ph
B(OH)2
C
2d, yield 11%
without adding
any substrates
F
I
+
N
F
H
N
Ullmann coupling
PdCl2, PPh3, Et3N
Cs2CO3,DMA
150 oC, 24 h
5c, NMR yield 65%
General procedure for substitution-Sonogashira coupling process.
A mixture of 4-fluoro-iodobenzene (1.0 mmol), carbazoles (0.5
mmol), Cs2CO3 (0.05 mmol) was added to a glass vial in solvent (1
mL) under air atmosphere. The reaction mixture was heated to 150
°C for 24 h. The reaction mixture was cooled to room temperature.
To this mixture was added arylacetylene (1.0 mmol), palladium
sources (0.025 mmol), PPh3 (0.05 mmol), CuI (0.0125 mmol), and
Et3N (1 mmol), and the mixture was heated to 130 °C for 6 h. The
reaction mixture was added to brine (15 mL) and extracted three
times with dichloromethane (3×15 mL). The solvent was
concentrated under vacuum and the product was isolated by short
chromatography on a silica gel (200–300 mesh) column.
One pot method
mixture
+
N
I
Sonogashira coupling
PdCl2, PPh3, CuI
Et3N, Cs2CO3,DMA
150 oC, 24 h
Ph
5d, NMR yield 12%
N
3a, 85%
Figure 2 Trial experiments for the one-pot synthesis of N-
arylcarbazole-based skeleton.
One-pot four-compound competing reaction was conducted as
shown in Figure 3. The reaction processes were composed of
competing reactions, namely, Suzuki coupling reaction,
Sonogashira coupling reaction and Ullmann coupling reaction.
The one-pot procedure for N-arylation and Pd-catalysed
Sonogashira performed coupling smoothly and produced good
yield (Figure 3).
General procedure for substitution-Ullmann coupling process. A
mixture of 4-fluoro-iodobenzene (1.0 mmol), carbazoles (0.5 mmol),
Cs2CO3 (0.05 mmol) was added to a glass vial in solvent (1 mL)
under air atmosphere. The reaction mixture was heated to 150 °C
for 24 h. The reaction mixture was cooled to room temperature. To
this mixture was added palladium sources (0.025 mmol), PPh3 (0.05
mmol), CuI (0.0125 mmol), and Et3N (1 mmol), and the mixture was
heated to 130 °C for 6 h. The reaction mixture was added to brine
(15 mL) and extracted three times with dichloromethane (3×15 mL).
The solvent was concentrated under vacuum and the product was
isolated by short chromatography on a silica gel (200–300 mesh)
column.
9-([1,1'-Biphenyl]-4-yl)-9H-carbazole (2a).4c Purification by flash
chromatography (petroleum ether): a white solid (145 mg, 91%),
mp = 227-228 °C; 1H NMR (400 MHz, CDCl3): δ 8.19 (dd, J = 1.2 Hz, J
= 0.8 Hz, 1H), 8.17 (dd, J = 1.2 Hz, J = 0.8 Hz, 1H), 7.86-7.83 (m, 2H),
7.73-7.70 (m, 2H), 7.68-7.65 (m, 2H), 7.55-7.41 (m, 7H), 7.35-7.31
(m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.81, 140.26, 140.23,
136.82, 128.91, 128.46, 127.60, 127.28, 127.10, 125.91, 123.38,
120.28, 119.92, 109.79, ppm.
Figure 3 One-pot competing reaction.
Experimental
General experimental methods. All reactions were performed in
glass vial under air atmosphere. DMF, DMSO, DMA, and NMP were
distilled from 4Å-molecular sieves. Other reagents were purchased
from commercial sources used without additional purification. NMR
spectra were recorded on a Bruke Avance III HD 400 spectrometer
9-(4'-Methyl-[1,1'-biphenyl]-4-yl)-9H-carbazole (2b). Purification by
flash chromatography (petroleum ether): a white solid (135 mg,
81%), mp = 235-236 °C; 1H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 8.0
Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.67-7.62 (m, 4H), 7.53-7.45 (m, 4H),
7.36-7.32 (m, 4H), 2.48 (s, 3H), ppm; 13C NMR (100 MHz, CDCl3): δ
140.93, 140.28, 137.52, 137.42, 136.60, 129.72, 128.31, 127.34,
127.00, 125.99, 123.44, 120.35, 119.97, 109.90, 21.21, ppm; HRMS
(EI): m/z calcd for C25H19N [M]+ 333.1517, found 333.1520.
1
using TMS as internal standard (400 MHz for H NMR, 100 MHz for
13C NMR and 376 MHz for 19F NMR). The Mass data of the
compounds were collected on
a Bruker ultrafleXtreme mass
spectrometer. All products were isolated by short chromatography
on a silica gel (200–300 mesh) column.
6 | J. Name., 2012, 00, 1-3
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9-(4'-Propyl-[1,1'-biphenyl]-4-yl)-9H-carbazole (2c). Purification by 130.69, 130.58, 129.88, 127.66, 126.66, 126.02, 125.99, 123.46,
flash chromatography (petroleum ether): a white solid (161 mg, 120.38, 120.01, 109.92, 20.66, ppm; HRMS (EI): m/z calcd for
89%), mp = 161-162 °C; 1H NMR (400 MHz, CDCl3): δ 8.19 (d, J = 7.6 C25H19N [M]+ 333.1517, found 333.1520.
Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.64 (q, J = 4.0 Hz, 4H), 7.51-7.43 (m,
4H), 7.36-7.31 (m, 4H), 2.70 (t, J = 7.6 Hz, 2H), 1.75 (sext, J = 7.6 Hz, 9-([1,1'-Biphenyl]-3-yl)-9H-carbazole (2i).9 Purification by flash
2H), 1.03 (t, J = 7.2 Hz, 3H), ppm; 13C NMR (100 MHz, CDCl3): δ chromatography (petroleum ether): a white solid (140 mg, 88%),
1
142.31, 140.90, 140.30, 137.62, 136.55, 129.09, 128.30, 127.30, mp = 113-115 °C; H NMR (400 MHz, CDCl3): δ 8.21 (d, J = 7.6 Hz,
126.96, 125.94, 123.40, 120.30, 119.92, 109.86, 37.74, 24.57, 13.91, 2H), 7.85 (t, J = 2.0 Hz, 1H), 7.75-7.68 (m, 4H), 7.61-7.58 (m, 1H),
ppm; HRMS (EI): m/z calcd for C27H23N [M]+ 361.1830, found 7.53-7.40 (m, 7H), 7.36-7.32 (m, 2H), ppm; 13C NMR (100 MHz,
361.1834.
CDCl3): δ 143.14, 140.90, 140.14, 138.24, 130.28, 128.98, 127.87,
127.19, 126.14, 126.00, 125.83, 125.75, 123.43, 120.36, 119.99,
9-(4'-Fluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole (2d).8 Purification by 109.84, ppm.
flash chromatography (petroleum ether): a white solid (98 mg, 58%),
mp = 186-187 °C; 1H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 7.6 Hz, 9-(4'-Methyl-[1,1'-biphenyl]-3-yl)-9H-carbazole (2j). Purification by
2H), 7.80 (d, J = 8.4 Hz, 2H), 7.70-7.66 (m, 4H), 7.51-7.44 (m, 4H), flash chromatography (petroleum ether): a white solid (128 mg,
7.34 (t, J = 8.0 Hz, 2H), 7.23 (t, J = 8.4 Hz, 2H), ppm; 13C NMR (100 77%), mp = 72-73 °C; 1H NMR (400 MHz, CDCl3): δ 8.21 (d, J = 7.6 Hz,
MHz, CDCl3): δ 162.69 (d, JC-F = 245.4 Hz), 140.85, 139.32, 136.91, 2H), 7.84 (t, J = 2.0 Hz, 1H), 7.74-7.68 (m, 2H), 7.61-7.45 (m, 7H),
136.42 (d, JC-F = 3.2 Hz), 128.74 (d, JC-F = 8.0 Hz), 128.40, 127.41, 7.37-7.31 (m, 4H), 2.45 (s, 3H), ppm; 13C NMR (100 MHz, CDCl3): δ
126.01, 123.47, 120.37, 120.04, 115.89 (d, JC-F = 21.3 Hz), 109.81, 143.07, 140.92, 138.19, 137.76, 137.27, 130.23, 129.71, 127.02,
ppm; 19F NMR (376 MHz, CDCl3): δ -115.04, ppm; HRMS (MALDI): 126.00, 125.94, 125.53, 123.43, 120.36, 119.97, 109.89, 21.17, ppm;
m/z calcd for C24H16FN [M]+ 337.1261, found 337.1263.
HRMS (EI): m/z calcd for C25H19N [M]+ 333.1517, found 333.1520.
9-(4'-(Trifluoromethyl)-[1,1'-biphenyl]-4-yl)-9H-carbazole
(2e). 9-(4'-Fluoro-[1,1'-biphenyl]-3-yl)-9H-carbazole (2k). Purification by
Purification by flash chromatography (petroleum ether): a white flash chromatography (petroleum ether): a white solid (108 mg,
1
solid (132 mg, 68%), mp = 251-252 °C; H NMR (400 MHz, CDCl3): δ 64%), mp = 67 °C; 1H NMR (400 MHz, CDCl3): δ 8.25-8.22 (m, 2H),
8.20 (d, J = 7.6 Hz, 2H), 7.87-7.78 (m, 6H), 7.72 (d, J = 8.4 Hz, 2H), 7.85-7.81 (m, 1H), 7.73-7.59 (m, 5H), 7.55-7.46 (m, 4H), 7.40-7.35
7.53-7.45 (m, 4H), 7.35 (t, J = 8.0 Hz, 2H), ppm; 13C NMR (100 MHz, (m, 2H), 7.23-7.18 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ
CDCl3): δ 143.76, 140.72, 138.71, 137.82, 128.72, 127.49, 127.43, 162.81 (d, JC-F = 245.8 Hz), 142.16, 140.91, 138.35, 136.27 (d, JC-F
=
126.05, 125.95, 125.91, 123.54, 120.40, 120.16, 109.77, 29.72, ppm; 3.3 Hz), 130.40, 129.74, 128.82 (d, JC-F = 8.0 Hz), 127.04, 126.08,
19F NMR (376 MHz, CDCl3): δ -62.41, ppm.
126.00, 125.87, 125.62, 123.50, 120.44, 120.10, 115.93 (d, JC-F =
21.4 Hz), 109.82, ppm; 19F NMR (376 MHz, CDCl3): δ -114.60 - -
9-(3',4',5'-Trifluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole
(2f). 114.62 (m), ppm; HRMS (MALDI): m/z calcd for C24H16FN [M]+
Purification by flash chromatography (petroleum ether): a white 337.1261, found 337.1263.
1
solid (125 mg, 67%), mp = 184-185 °C; H NMR (400 MHz, CDCl3): δ
8.22-8.19 (m, 2H), 7.76-7.68 (m, 4H), 7.51-7.45 (m, 4H), 7.38-7.30 9-([1,1'-Biphenyl]-2-yl)-9H-carbazole (2l). Purification by flash
(m, 4H), ppm; 13C NMR (100 MHz, CDCl3): δ 151.66 (ddd, JC-F = 248.4 chromatography (petroleum ether): a white solid (147 mg, 92%),
1
Hz, JC-F = 10.0 Hz, JC-F = 4.3 Hz), 140.67, 138.01, 137.07 (dd, JC-F = 3.7 mp = 152-153 °C; H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 7.6 Hz,
Hz, JC-F = 2.1 Hz), 136.39 (ddd, JC-F = 12.4 Hz, JC-F = 7.7 Hz, JC-F = 4.6 2H), 7.71 (dd, J = 7.2 Hz, J = 1.6 Hz, 1H), 7.65-7.51 (m, 3H), 7.32-7.29
Hz), 128.33, 128.32, 127.52, 126.13, 123.61, 120.46, 120.29, 111.13 (m, 2H), 7.23-7.19 (m, 2H), 7.12-7.00 (m, 7H), ppm; 13C NMR (100
(dd, JC-F = 16.0 Hz, JC-F = 6.1 Hz), 109.74, ppm; 19F NMR (376 MHz, MHz, CDCl3): δ 141.15, 141.08, 138.61, 134.80, 131.55, 129.80,
CDCl3): δ -133.58 (d, JF-F = 20.3 Hz), 161.89 (t, JF-F = 20.3 Hz), ppm.
128.80, 128.74, 128.07, 127.76, 127.25, 125.62, 123.06, 120.04,
119.44, 109.98, ppm; HRMS (EI): m/z calcd for C24H17N [M]+
9-(3'-Methyl-[1,1'-biphenyl]-4-yl)-9H-carbazole (2g). Purification by 319.1361, found 319.1369.
flash chromatography (petroleum ether): a white solid (160 mg,
96%), mp = 153-154 °C; 1H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 7.6 9-([1,1'-Biphenyl]-4-yl)-3,6-di-tert-butyl-9H-carbazole
(2m).
Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.8 Hz, 2H), 7.55-7.41 (m, Purification by flash chromatography (petroleum ether): a white
7H), 7.36-7.32 (m, 2H), 7.26 (d, J = 7.6 Hz, 2H), 2.51 (s, 3H), ppm; 13 solid (175 mg, 81%), mp = 185-186 °C; 1H NMR (400 MHz, CDCl3): δ
C
NMR (100 MHz, CDCl3): δ 140.89, 140.47, 140.29, 138.58, 136.77, 8.20 (s, 2H), 7.84 (d, J = 8.0 Hz, 2H), 7.73 (), (d, J = 8.0 Hz, 2H), 7.67
128.87, 128.53, 128.40, 127.98, 127.29, 125.96, 124.26, 123.42, (d, J = 8.0 Hz, 2H), 7.56-7.51 (m, 4H), 7.45 (d, J = 8.8 Hz, 3H), 1.52 (d,
120.33, 119.95, 109.86, 21.61, ppm; HRMS (EI): m/z calcd for J = 1.6 Hz, 18H), ppm; 13C NMR (100 MHz, CDCl3): δ 142.95, 140.40,
C25H19N [M]+ 333.1517, found 333.1520.
139.80, 139.28, 137.44, 128.98, 128.43, 127.60, 127.16, 126.97,
123.69, 123.49, 116.31, 109.35, 34.82, 32.11, ppm.
9-(2'-Methyl-[1,1'-biphenyl]-4-yl)-9H-carbazole (2h). Purification by
flash chromatography (petroleum ether): a white solid (104 mg, 9-([1,1'-Biphenyl]-4-yl)-3-bromo-9H-carbazole (2n).10 Purification
65%), mp = 140-141 °C; 1H NMR (400 MHz, CDCl3): δ 8.21 (d, J = 8.0 by flash chromatography (petroleum ether): a white solid (135 mg,
Hz, 2H), 7.67-7.46 (m, 8H), 7.41-7.33 (m, 6H), 2.44 (s, 3H), ppm; 13
C
68%), mp = 153-154 °C; 1H NMR (400 MHz, CDCl3): δ 8.31 (d, J = 1.6
NMR (100 MHz, CDCl3): δ 141.12, 141.08, 140.93, 136.40, 135.45, Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 8.4 Hz, 2H), 7.74-7.71 (m,
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2H), 7.62 (d, J = 8.4 Hz, 2H), 7.57-7.53 (m, 3H), 7.50-7.44 (m, 3H), 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 145.01, 140.60, 137.38,
7.37 (d, J = 8.4 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 141.22, 133.06, 131.68, 128.03, 126.85, 126.06, 123.55, 122.54, 120.37,
140.67, 140.14, 139.55, 136.38, 129.03, 128.67, 128.64, 127.79, 120.19, 109.77, 90.59, 88.04, 28.90, 15.39, ppm; HRMS (EI): m/z
127.26, 127.17, 126.75, 125.20, 123.10, 122.38, 120.55, 120.43, calcd for C28H21N [M]+ 371.1674, found 371.1680.
112.79, 111.37, 110.12, ppm.
9-(4-((4-Chlorophenyl)ethynyl)phenyl)-9H-carbazole
(3d).
9-([1,1'-Bphenyl]-4-yl)-3,6-dibromo-9H-carbazole (2o). Purification Purification by flash chromatography (petroleum ether): a white
by flash chromatography (petroleum ether): a white solid (174 mg, solid (117 mg, 62%), mp = 234-235 °C; 1H NMR (400 MHz, CDCl3): δ
73%), mp = 218-219 °C; 1H NMR (400 MHz, CDCl3): δ 8.23 (d, J = 1.6 8.18 (d, J = 7.6 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H), 7.61 (d, J = 8.4 Hz,
Hz, 2H), 7.84 (d, J = 8.8 Hz, 2H), 7.72-7.69 (m, 2H), 7.59-7.52 (m, 6H), 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.48-7.43 (m, 4H), 7.39 (d, J = 8.4 Hz,
7.47-7.43 (m, 1H), 7.34 (d, J = 8.8 Hz, 2H), ppm; 13C NMR (100 MHz, 2H), 7.35-7.31 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.52,
CDCl3): δ 141.03, 139.98, 139.85, 135.88, 129.43, 129.03, 128.74, 137.80, 134.55, 133.12, 132.89, 128.80, 126.88, 126.08, 123.59,
127.87, 127.18, 127.16, 124.01, 123.25, 113.14, 111.59, ppm; HRMS 121.89, 121.55, 120.40, 120.27, 109.73, 89.61, 89.18, ppm; HRMS
(EI): m/z calcd for C24H15Br2N [M]+ 474.9571, found 474.9580.
(EI): m/z calcd for C26H16ClN [M]+ 377.0971, found 377.0975.
9-([1,1'-Biphenyl]-4-yl)-2,7-dibromo-9H-carbazole (2p). Purification 9-(4-((4-Fluorophenyl)ethynyl)phenyl)-9H-carbazole
(3e).
by flash chromatography (petroleum ether): a white solid (155 mg, Purification by flash chromatography (petroleum ether): a white
1
65%), mp = 199-201 °C; 1H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.4 solid (92 mg, 51%), mp = 254 °C; H NMR (400 MHz, CDCl3): δ 8.18
Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 7.6 Hz, 2H), 7.60-7.53 (m, (d, J = 7.6 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H), 7.62-7.58 (m, 4H), 7.48-
6H), 7.47-7.43 (m, 3H), ppm; 13C NMR (100 MHz, CDCl3): δ 141.89, 7.43 (m, 4H), 7.35-7.31 (m, 2H), 7.11 (t, J = 8.4 Hz, 2H), ppm; 13C
141.37, 139.99, 135.49, 129.02, 128.92, 127.88, 127.34, 127.22, NMR (100 MHz, CDCl3): δ 162.67 (d, JC-F = 248.5 Hz), 140.56, 137.67,
123.69, 121.75, 121.50, 120.04, 113.12, ppm; HRMS (EI): m/z calcd 133.60 (d, JC-F = 8.3 Hz), 133.08, 126.89, 126.09, 123.60, 122.09,
for C24H15Br2N [M]+ 474.9571, found 474.9580.
120.41, 120.27, 119.16 (d, JC-F = 3.6 Hz), 115.78 (d, JC-F = 21.9 Hz),
109.75, 89.26, 88.39 (d, JC-F = 1.5 Hz), ppm.
4-Fluoro-4'-methoxy-1,1'-biphenyl (2q).11 Purification by flash
chromatography (petroleum ether): a white solid (138 mg, 68%), 9-(4-(m-Tolylethynyl)phenyl)-9H-carbazole (3f).8 Purification by
mp = 79 °C; 1H NMR (400 MHz, CDCl3): δ 7.53-7.48 (m, 4H), 7.12 (t, J flash chromatography (petroleum ether): a white solid (109 mg,
= 8.8 Hz, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.87 (s, 3H), pmm; 13C NMR 61%), mp = 109-110 °C; 1H NMR (400 MHz, CDCl3): δ 8.18 (d, J = 8.0
(100 MHz, CDCl3): δ 162.09 (d, JC-F = 244.0 Hz), 159.11, 136.96 (d, JC-F Hz, 2H), 7.81-7.77 (m, 2H), 7.62-7.59 (m, 2H), 7.50-7.42 (m, 6H),
= 3.3 Hz), 132.84, 128.21 (d, JC-F = 7.8 Hz), 128.03, 115.52 (d, JC-F
=
7.36-7.29 (m, 3H), 7.22 (d, J = 7.6 Hz, 1H), 2.42 (s, 3H), ppm; 13C
NMR (100 MHz, CDCl3): δ 140.61, 138.18, 137.53, 133.14, 132.31,
129.48, 128.84, 128.40, 126.88, 126.12, 123.61, 122.90, 122.43,
21.1 Hz), 114.25, 55.37, ppm.
9-(4-(Phenylethynyl)phenyl)-9H-carbazole (3a).6a Purification by 120.43, 120.27, 109.81, 90.61, 88.42, 21.34, ppm; HRMS (MALDI):
flash chromatography (petroleum ether): a white solid (160 mg, m/z calcd for C27H19N [M]+ 357.1512, found 357.1513.
1
93%), mp = 137-138 °C; H NMR (400 MHz, CDCl3): δ 8.17 (t, J = 1.2
Hz, 1H), 8.15 (dd, J = 1.2 Hz, J = 0.8 Hz, 1H), 7.79 (t, J = 2.0 Hz, 1H), 9-(4-((3-Fluorophenyl)ethynyl)phenyl)-9H-carbazole
(3g).
7.77 (t, J = 2.0 Hz, 1H), 7.62-7.58 (m, 4H), 7.46-7.38 (m, 7H), 7.34- Purification by flash chromatography (petroleum ether): a white
7.30 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.51, 137.50, solid (139 mg, 77%), mp = 134-135 °C; 1H NMR (400 MHz, CDCl3): δ
133.06, 131.63, 128.45, 128.38, 126.80, 126.00, 123.49, 122.98, 8.18 (d, J = 7.6 Hz, 2H), 7.79 (d, J = 8.8 Hz, 2H), 7.62 (d, J = 8.4 Hz,
122.23, 120.31, 120.15, 109.69, 90.26, 88.60, ppm.
2H), 7.49-7.43 (m, 4H), 7.40-7.29 (m, 5H), 7.14-7.08 (m, 1H), ppm;
13C NMR (100 MHz, CDCl3): δ 162.45 (d, JC-F = 245.1 Hz), 140.52,
9-(4-(p-Tolylethynyl)phenyl)-9H-carbazole (3b). Purification by 137.91, 133.21, 130.03 (d, JC-F = 8.6 Hz), 127.57 (d, JC-F = 3.1 Hz),
flash chromatography (petroleum ether): a white solid (170 mg, 126.88, 126.09, 124.90 (d, JC-F = 9.4 Hz), 123.60, 121.74, 120.30 (d,
95%), mp = 200-201 °C; 1H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 7.6 JC-F = 11.7 Hz), 118.46 (d, JC-F = 22.7 Hz), 115.81 (d, JC-F = 21.1 Hz),
Hz, 2H), 7.78 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.52-745 (m, 109.74, 89.54, 89.01 (d, JC-F = 3.3 Hz), ppm.
6H), 7.35-7.31 (m, 2H), 7.22 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H), ppm; 13
C
NMR (100 MHz, CDCl3): δ 140.59, 138.70, 137.37, 133.04, 131.58, 9-(2-(Phenylethynyl)phenyl)-9H-carbazole (3h). Purification by
129.21, 126.85, 126.05, 123.53, 122.52, 120.36, 120.18, 119.95, flash chromatography (petroleum ether): a white solid (149 mg,
109.76, 90.54, 88.03, 21.57, ppm; HRMS (EI): m/z calcd for C27H19N 87%), mp = 108-109 °C; 1H NMR (400 MHz, CDCl3): δ 8.27 (d, J = 8.4
[M]+ 357.1512, found 357.1513.
Hz, 2H), 7.87 (dd, J = 8.0 Hz, J = 1.6 Hz, 2H), 7.68-7.54 (m, 3H), 7.51-
7.47 (m, 2H), 7.41-7.37 (m, 4H), 7.23-7.12 (m, 3H), 6.71 (dd, J = 8.4
(3c). Hz, J = 1.6 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 141.04,
9-(4-((4-Ethylphenyl)ethynyl)phenyl)-9H-carbazole
Purification by flash chromatography (petroleum ether): a white 139.13, 133.47, 131.38, 129.50, 129.08, 128.38, 128.16, 128.08,
1
solid (152 mg, 82%), mp = 191-192 °C; H NMR (400 MHz, CDCl3): δ 125.89, 123.48, 123.09, 122.61, 120.32, 119.94, 110.70, 95.57,
8.18 (d, J = 8.0 Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 8.4 Hz, 86.24, ppm; HRMS (EI): m/z calcd for C26H17N [M]+ 343.1361, found
2H), 7.54 (d, J = 8.0 Hz, 2H), 7.49-7.43 (m, 4H), 7.35-7.31 (m, 2H), 343.1362.
7.25 (d, J = 8.0 Hz, 2H), 2.72 (q, J = 7.6 Hz, 2H), 1.30 (t, J = 7.6 Hz,
8 | J. Name., 2012, 00, 1-3
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3,6-Di-tert-butyl-9-(4-(phenylethynyl)phenyl)-9H-carbazole (3i).6a 120.06, 109.73, 95.61, 79.90, 32.71, 29.74, 25.95, 24.94, ppm;
Purification by flash chromatography (petroleum ether): a white HRMS (EI): m/z calcd for C26H23N [M]+ 349.1830, found 349.1839.
1
solid (188 mg, 87%), mp = 185-186 °C; H NMR (400 MHz, CDCl3): δ
8.16 (d, J = 2.0 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.62-7.58 (m, 4H), 9-(4-(Thiophen-3-ylethynyl)phenyl)-9H-carbazole (3o). Purification
7.50 (dd, J = 8.4 Hz, J = 2.0 Hz, 2H), 7.43-7.40 (m, 5H), 1.49 (s, 18H), by flash chromatography (petroleum ether): a white solid (168 mg,
1
ppm; 13C NMR (100 MHz, CDCl3): δ 143.21, 138.93, 138.13, 133.06, 96%), mp = 158 °C; H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 7.6 Hz,
131.70, 128.46, 126.42, 123.76, 123.61, 123.16, 121.69, 116.33, 2H), 7.77 (d, J = 7.6 Hz, 2H), 7.62-7.58 (m, 3H), 7.48-7.43 (m, 4H),
109.25, 90.16, 88.86, 34.80, 32.05, ppm.
7.38-7.27 (m, 4H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.56,
137.52, 133.02, 129.89, 128.95, 126.86, 126.06, 125.53, 123.55,
(3j). 122.23, 122.09, 120.37, 120.21, 109.75, 88.19, 85.46, ppm; HRMS
3-Bromo-9-(4-(phenylethynyl)phenyl)-9H-carbazole
Purification by flash chromatography (petroleum ether): a white (EI): m/z calcd for C24H15NS [M]+ 349.0925, found 349.0923.
1
solid (36 mg, 17%), mp = 206-207 °C; H NMR (400 MHz, CDCl3): δ
8.27 (d, J = 2.0 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 7.6 Hz, 9-(4-(Hept-1-yn-1-yl)phenyl)-9H-carbazole (3p). Purification by
2H), 7.62-7.53 (m, 5H), 7.48-7.40 (m, 5H), 7.36-7.32 (m, 2H), ppm; flash chromatography (petroleum ether): a white solid (91 mg, 54%),
13C NMR (100 MHz, CDCl3): δ 140.92, 139.26, 137.03, 133.21, mp = 60-61 °C; 1H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 7.6 Hz, 2H),
131.70, 128.74, 128.58, 128.45, 126.81, 126.80, 125.30, 123.13, 7.69 (dd, J = 8.4 Hz, J = 2.0 Hz, 2H), 7.55 (dd, J = 8.4 Hz, J = 1.6 Hz,
122.95, 122.71, 122.47, 120.62, 120.56, 112.98, 111.24, 109.98, 2H), 7.47 (d, J = 8.0 Hz, 4H), 7.38-7.33 (m, 2H), 2.53 (t, J = 7.2 Hz,
90.57, 88.48, ppm; HRMS (EI): m/z calcd for C26H16BrN [M]+ 2H), 1.73 (q, J = 6.8 Hz, 2H), 1.59-1.44 (m, 4H), 1.03 (d, J = 7.2 Hz,
421.0466, found 421.0473.
2H), ppm; 13C NMR (100 MHz, CDCl3): δ 140.72, 136.87, 133.10,
126.84, 126.07, 123.54, 123.31, 120.40, 120.15, 109.80, 91.71,
(3k). 80.05, 31.27, 28.55, 22.38, 19.56, 14.15, ppm.
3,6-Dibromo-9-(4-(phenylethynyl)phenyl)-9H-carbazole
Purification by flash chromatography (petroleum ether): a white
solid (13 mg, 5%), mp = 148-149 °C; 1H NMR (400 MHz, CDCl3): δ Fluoro-4-((4-methoxyphenyl)ethynyl)benzene (3q).12 Purification
8.22 (d, J = 2.0 Hz, 2H), 7.79 (d, J = 8.0 Hz, 2H), 7.62-7.60 (m, 2H), by flash chromatography (petroleum ether): a white solid (167 mg,
7.56-7.51 (m, 4H), 7.43-7.40 (m, 3H), 7.31 (d, J = 8.4 Hz, 2H), ppm; 74%), mp = 91-92 °C; 1H NMR (400 MHz, CDCl3): δ 7.53-7.47 (m, 4H),
13C NMR (100 MHz, CDCl3): δ 139.59, 136.51, 133.31, 131.70, 7.06 (t, J = 8.8 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), ppm.
129.53, 128.65, 128.46, 126.74, 124.13, 123.31, 123.14, 122.85,
113.35, 111.48, 90.80, 88.30, ppm.
2-(4-((4-Fluorophenyl)ethynyl)phenyl)acetonitrile (3r). Purification
by flash chromatography (petroleum ether): a white solid (66 mg,
(3l). 28%), mp = 94-95 °C; 1H NMR (400 MHz, CDCl3): δ 7.56-7.52 (m, 4H),
2,7-Dibromo-9-(4-(phenylethynyl)phenyl)-9H-carbazole
Purification by flash chromatography (petroleum ether): a white 7.35 (d, J = 8.0 Hz, 2H), 7.08 (t, J = 8.8 Hz, 2H), 3.80 (s, 2H), ppm; 13
C
=
1
solid (50 mg, 20%), mp = 228-229 °C; H NMR (400 MHz, CDCl3): δ NMR (100 MHz, CDCl3): δ 162.63 (d, JC-F = 248.5 Hz), 133.54 (d, JC-F
7.97 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.4 Hz, 2H), 7.63-7.61 (m, 2H), 8.3 Hz), 132.23, 129.90, 127.99, 123.4, 119.03 (d, JC-F = 34.6 Hz),
7.53 (d, J = 8.0 Hz, 4H), 7.45 (d, J = 1.6 Hz, 1H), 7.43-7.41 (m, 4H), 117.40, 115.72 (d, JC-F = 22.1 Hz), 89.17, 88.14, 23.60, ppm; 19F NMR
ppm; 13C NMR (100 MHz, CDCl3): δ 141.61, 136.12, 133.45, 131.73, (376 MHz, CDCl3): δ -110.52, ppm.
128.64, 128.46, 126.92, 123.90, 123.47, 122.87, 121.85, 121.54,
120.10, 113.05, 90.92, 88.26, ppm HRMS (EI): m/z calcd for Methyl 4-((4-fluorophenyl)ethynyl)benzoate (3s).13 Purification by
C26H15Br2N [M]+ 498.9571, found 498.9567.
flash chromatography (petroleum ether): a white solid (134 mg,
53%), mp = 104-105 °C; 1H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 8.0
(3m). Hz, 2H), 7.61-7.53 (m, 4H), 7.09 (t, J = 8.8 Hz, 2H), 3.95 (s, 3H), ppm.
9-(4-(Cyclohex-1-en-1-ylethynyl)phenyl)-9H-carbazoleb
Purification by flash chromatography (petroleum ether): a white
1
solid (149 mg, 86%), mp = 150-151 °C; H NMR (400 MHz, CDCl3): δ 9-(3'-Fluoro-[1,1'-biphenyl]-3-yl)-9H-carbazole (4a). Purification by
8.17 (d, J = 7.6 Hz, 2H), 7.68 (d, J = 8.8 Hz, 2H), 7.54 (d, J = 8.8 Hz, flash chromatography (petroleum ether): a white solid (94 mg, 56%),
2H), 7.45-7.44 (m, 4H), 7.35-7.30 (m, 2H), 6.33-630 (m, 1H), 2.33- mp = 128-129 °C; 1H NMR (400 MHz, CDCl3): δ 8.21 (dd, J = 8.0 Hz, J
2.28 (m, 2H), 2.24-2.19 (m, 2H), 1.78-1.65 (m, 4H), ppm; 13C NMR = 1.2 Hz, 2H), 7.83 (s, 1H), 7.74-7.70 (m, 2H), 7.65-7.61 (m, 1H),
(100 MHz, CDCl3): δ 140.61, 137.02, 135.73, 132.91, 126.78, 126.01, 7.52-7.45 (m, 6H), 7.40-7.33 (m, 3H), 7.16-7.09 (m, 1H), ppm; 13C
123.49, 122.86, 120.63, 120.33, 120.12, 109.75, 92.26, 86.09, 29.23, NMR (100 MHz, CDCl3): δ 163.27 (d, JC-F = 244.6 Hz), 142.38 (d, JC-F
=
25.84, 22.36, 21.53, ppm; HRMS (EI): m/z calcd for C26H21N [M]+ 7.6 Hz), 141.86 (d, JC-F = 2.2 Hz), 140.85, 138.40, 130.54, 130.46,
347.1674, found 347.1680.
126.43, 126.09, 126.07, 125.72, 123.49, 122.83 (d, JC-F = 2.8 Hz),
120.42, 120.10, 114.70 (d, JC-F = 21.0 Hz), 114.12 (d, JC-F = 22.0 Hz),
9-(4-(Cyclohexylethynyl)phenyl)-9H-carbazole (3n). Purification by 109.76, ppm; 19F NMR (376 MHz, CDCl3): δ -112.58, ppm; HRMS
flash chromatography (petroleum ether): a white solid (166 mg, (MALDI): m/z calcd for C24H16FN [M]+ 337.1261, found 337.1263.
95%), mp = 151-152 °C; 1H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 7.6
Hz, 2H), 7.66 (d, J = 8.8 Hz, 2H), 7.52 (d, J = 8.8 Hz, 2H), 7.46-7.41 (m, 9-(2'-Fluoro-[1,1'-biphenyl]-2-yl)-9H-carbazole (4b). Purification by
4H), 7.34-7.30 (m, 2H), 2.71-2.65 (m, 1H), 1.98-1.80 (m, 4H), 1.67- flash chromatography (petroleum ether): a colorless oil (32 mg,
1.57 (m, 4H), 1.47-1.38 (m, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 19%); 1H NMR (400 MHz, CDCl3): δ 8.05 (d, J = 8.0 Hz, 2H), 7.72-7.68
140.67, 136.75, 133.07, 126.78, 125.99, 123.45, 123.29, 120.33, (m, 1H), 7.65-7.56 (m, 3H), 7.35-7.30 (m, 2H), 7.23-7.16 (m, 4H),
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Journal Name
7.02-6.96 (m, 1H), 6.89-6.83 (m, 2H), 6.69-6.65 (m, 1H), ppm; 13C 9-(4'-Fluoro-[1,1'-biphenyl]-4-yl)-3-nitro-9H-carbazole
(4g).
NMR (100 MHz, CDCl3): δ 159.11 (d, JC-F = 245.3 Hz), 141.19, 135.83, Purification by flash chromatography (petroleum ether): a yellow
1
135.14, 132.46 (d, JC-F = 2.1 Hz), 130.22 (d, JC-F = 3.1 Hz), 129.59, solid (92 mg, 48%), mp = 189 °C; H NMR (400 MHz, CDCl3): δ 9.12
129.46, 129.33 (d, JC-F = 8.2 Hz), 128.28, 125.64, 123.58 (d, JC-F = 3.6 (d, J = 2.4 Hz, 1H), 8.37 (dd, J = 9.2 Hz, J = 2.4 Hz, 1H), 8.25 (d, J = 8.0
Hz), 123.05, 120.00, 119.53, 115.51 (d, JC-F = 22.1 Hz), 109.85, Hz, 1H), 7.84 (d, J = 8.9 Hz, 2H), 7.70-7.63 (m, 4H), 7.50-7.43 (m, 4H),
109.84; 19F NMR (376 MHz, CDCl3): δ -116.28, ppm; HRMS (MALDI): 7.24 (t, J = 8.8 Hz, 2H), ppm; 13C NMR (100 MHz, CDCl3): δ 162.86 (d,
m/z calcd for C24H16FN [M]+ 337.1261, found 337.1263.
JC-F = 246.1 Hz), 143.93, 142.33, 141.50, 140.64, 136.00 (d, JC-F = 4.0
Hz), 135.44, 128.82 (d, JC-F = 8.1 Hz), 128.76, 127.70, 127.47, 123.21,
3,6-Di-tert-butyl-9-(4'-fluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole
123.09, 121.88, 121.68, 120.98, 117.34, 116.12, 115.96 (d, JC-F =
(4c). Purification by flash chromatography (petroleum ether): a 21.4 Hz), 110.71, 109.57, ppm; 19F NMR (376 MHz, CDCl3): δ -114.47,
white solid (63 mg, 28%), mp = 192 °C; 1H NMR (400 MHz, CDCl3): δ ppm.
8.18 (d, J = 1.6 Hz, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.69-7.64 (m, 4H),
7.50 (dd, J = 8.8 Hz, J = 2.0 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.21 (t, J
= 8.4 Hz, 2H), 1.50 (s, 18H), ppm; 13C NMR (100 MHz, CDCl3): δ
142.94, 139.18, 138.76, 137.41, 136.50 (d, JC-F = 3.1 Hz), 128.68 (d,
JC-F = 8.0 Hz), 128.26 (d, JC-F = 0.6 Hz), 126.98, 123.63, 123.43,
116.27, 115.82 (d, JC-F = 21.3 Hz), 109.22, 34.76, 32.03, ppm; 19F
NMR (376 MHz, CDCl3): δ -115.29, ppm; HRMS (EI): m/z calcd for
C32H32FN [M]+ 449.2519, found 449.2528.
Conclusions
We developed a series of efficient one-pot N-arylation and Pd-
catalysed cross-coupling procedure to produce a carbazole-
based skeleton with good yield and high selectivity. The
carbazole-based
skeleton
contained
biphenyl
and
diarylacetylene cores. A wide range of functional groups,
including aryl acetylene, boronic acid, and fluorinated
iodobenzene, are compatible in the developed one-pot
reaction conditions. The use of metal-free N-arylation is the
key starting reaction to form iodinated N-arylcarbazole which
is not isolated, but submitted to further structure elongation.
N-Arylation and Pd-catalysed Sonogashira coupling via one-pot
process was successfully obtained in contrast to N-arylation
and Pd-catalysed Suzuki or Ullmann coupling. The Pd-catalyst
3-Bromo-9-(4'-fluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole
(4d).
Purification by flash chromatography (petroleum ether): a white
1
solid (89 mg, 43%), mp = 189-190 °C; H NMR (400 MHz, CDCl3): δ
8.29 (d, J = 2.0 Hz, 1H), 8.13 (d, J = 7.6 Hz, 1H), 7.79 (d, J = 8.8 Hz,
2H), 7.68-7.61 (m, 4H), 7.53 (dd, J = 8.8 Hz, J = 2.0 Hz, 1H), 7.48-7.47
(m, 2H), 7.36-7.32 (m, 2H), 7.22 (t, J = 8.8 Hz, 2H), ppm; 13C NMR
(100 MHz, CDCl3): δ 162.74 (d, JC-F = 145.7 Hz), 141.18, 139.69,
139.52, 136.40, 136.26 (d, JC-F = 3.3 Hz), 128.79, 128.68 (d, JC-F = 4.4
activated the C–I bond of fluorinated iodobenzene to decrease
Hz), 128.50, 127.33, 126.73, 125.19, 123.10, 122.37, 120.49 (d, JC-F
=
reaction selectivity, which is responsible for the poor results.
The competing reaction showed that N-arylation and Pd-
catalysed Sonogashira coupling was superior among the one-
pot four-compound processes.
9.9 Hz), 116.02, 115.81, 112.79, 111.29, 110.04, ppm; 19F NMR (376
MHz, CDCl3): δ -114.87, ppm; HRMS (EI): m/z calcd for C24H15BrFN
[M]+ 415.0372, found 415.0374.
3,6-Dibromo-9-(4'-fluoro-[1,1'-biphenyl]-4-yl)-9H-carbazole (4e).
Purification by flash chromatography (petroleum ether): a white
solid (111 mg, 45%), mp = 217 °C; 1H NMR (400 MHz, CDCl3): δ 8.22
(d, J = 2.0 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H), 7.67-7.64 (m, 2H), 7.58-
7.53 (m, 4H), 7.32 (d, J = 8.8 Hz, 2H), 7.22 (d, J = 8.8 Hz, 2H), ppm;
13C NMR (100 MHz, CDCl3): δ 162.78 (d, JC-F = 245.9 Hz), 140.04,
139.83, 136.10 (d, JC-F = 3.3 Hz), 135.91, 129.45, 128.76 (d, JC-F = 8.1
Hz), 128.61, 127.25, 124.02, 123.27, 115.96 (d, JC-F = 21.5 Hz),
113.17, 111.53, ppm; 19F NMR (376 MHz, CDCl3): δ -114.65, ppm;
Acknowledgements
The authors thank the financial support from the National
Natural Science Foundation of China (grant number
21466033).
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the
matter under discussion, limited experimental and spectral data,
and crystallographic data.
HRMS (EI): m/z calcd for
492.9474.
C
24H14Br2FN [M]+ 492.9477, found
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1
solid (97 mg, 39%), mp = 172-173 °C; H NMR (400 MHz, CDCl3): δ
3
7.98 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.8 Hz, 2H), 7.69-7.66 (m, 2H),
7.60-7.56 (m, 4H), 7.44 (dd, J = 8.4 Hz, J = 2.0 Hz, 2H), 7.23 (t, J = 8.4
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