Copper(I) iodide-catalyzed synthesis of 4-aryl-1 H -1,2,3-triazoles from anti -3-aryl-2,3-dibromopropanoic acids and sodium azide

Article abstract of DOI:10.1055/s-0030-1258312

4-Aryl-1H-1,2,3-triazoles were synthesized from anti-3-aryl-2,3- dibromopropanoic acids and sodium azide by using inexpensive copper(I) iodide as the catalyst in dimethyl sulfoxide

Full text of DOI:10.1055/s-0030-1258312

4256
PAPER
Copper(I) Iodide-Catalyzed Synthesis of 4-Aryl-1H-1,2,3-triazoles from
anti-3-Aryl-2,3-dibromopropanoic Acids and Sodium Azide
4
-Aryl-1
H
-1,2,3-tr
u
iazoles bo Jiang,a Chunxiang Kuang,*a Qing Yangb
a
Department of Chemistry, Tongji University, Siping Road 1239, Shanghai 200092, P. R. of China
Department of Biochemistry, School of Life Sciences, Fudan University, Handan Road 220, Shanghai 200433, P. R. of China
Fax +86(21)65983191; E-mail: kuangcx@tongji.edu.cn
b
Received 27 August 2010; revised 4 October 2010
bromopropanoic acids and sodium azide using the same
catalyst system.16 Both these methods require expensive
catalysts and suffer from long reaction times. We now re-
port our recent studies on the synthesis of 4-aryl-1H-
1,2,3-triazoles from readily available anti-3-aryl-2,3-di-
bromopropanoic acids by using inexpensive copper(I) io-
dide as a catalyst to give reaction times of as little as four
hours (Scheme 1).
Abstract: 4-Aryl-1H-1,2,3-triazoles were synthesized from anti-3-
aryl-2,3-dibromopropanoic acids and sodium azide by using inex-
pensive copper(I) iodide as the catalyst in dimethyl sulfoxide.
Key words: cyclizations, catalysis, heterocycles, azides, triazoles
Since the development of ‘click chemistry’ from the
Huisgen 1,3-dipolar cycloaddition of azides and alkynes
in the early 2000s,1 the synthesis of 1,2,3-triazoles has
grown in importance in medicinal,2 materials,3 and
biological4 research. Furthermore, a number of these com-
pounds show a broad spectrum of biological activities,
displaying, for example, antibacterial,5 herbicidal, fungi-
cidal,6 antiallergic,7 or anti-HIV8 properties. Recently,
1,2,3-triazoles have also been used as catalysts and
ligands in transition metal-based catalyst systems.9 The
rapidly growing demand for these heterocycles necessi-
tates the development of effective methods for the prepa-
ration of a range of 1,2,3-triazole derivatives.
Pd2(dba)3/Xantphos
90–110 °C, 36 h
Br
previous method
N
N
CO2H
NH
NaN3
+
Ar
Ar
CuI, base
Br
this method
Scheme 1
To identify suitable reaction conditions, we used anti-2,3-
dibromo-3-phenylpropanoic acid (1a) as a model sub-
strate with sodium azide. Initially, toluene and dioxane
were chosen as solvents and the reaction was performed at
110 °C for 24 hours with potassium carbonate as the base.
Products were isolated, albeit in somewhat low yields,
when a catalyst system consisting of 10% copper(I) iodide
and 20% of sodium ascorbate was used (Table 1, entries
1–2). We obtained moderate yields in shorter reaction
times of six to eight hours when N,N-dimethylformamide
was used as the solvent (Table 1, entries 3–4). To our de-
light, the yield increased to 65% when the reaction was
conducted in dimethyl sulfoxide with potassium carbon-
ate as the base (Table 1, entry 5). Inspired by this result,
we examined other bases such as cesium carbonate, tripo-
tassium phosphate, and potassium bicarbonate in dimeth-
yl sulfoxide. Cesium carbonate was identified as the best
Although the vigorous ‘click chemistry’ of copper(I)-cat-
alyzed [3+2]-cycloaddition reactions of organic azides
and terminal alkynes is capable of producing 1,4-disubsti-
tuted 1,2,3-triazoles regioselectively under mild condi-
tions,10 it has a limitation in that it has a reduced efficiency
in the case of inorganic azides. As a result, 4-monosubsti-
tuted 1H-1,2,3-triazoles cannot be prepared directly by
means of a click-chemistry strategy, and their preparation
requires a sequence involving deprotection steps and the
use of more elaborate azides.11 Other routes to 1H-1,2,3-
triazoles include dipolar cycloadditions between sodium
azide and alkynes bearing electron-withdrawing substitu-
ents,12 the reactions of sodium azide with nitroalkenes,13
and the rearrangement of propargyl azides.14
In 2006, Barluenga and co-workers15 reported a new base (Table 1, entries 6–8). The necessity of the using
method for the synthesis of 1H-triazoles from (E)-b- copper(I) iodide was obvious, as no product was obtained
arylvinyl bromides and sodium azide catalyzed by a in its absence (Table 1, entry 10). On the other hand, sodi-
tris(dibenzylideneacetone)dipalladium/Xantphos
[4,5- um ascorbate also appeared to play an important role in
bis(diphenylphosphino)-9,9-dimethylxanthene] catalyst the reaction, as the yield decreased in its absence (Table 1,
system. This efficient transformation affords 4-aryl-1H- entry 9). This may be because the copper(I) species is sta-
1,2,3-triazoles in near-quantitative yields. Recently, we bilized by sodium ascorbate in the system. As expected,
reported an interesting one-pot synthesis of 4-aryl-1H- only a trace of product was obtained when the temperature
1,2,3-triazoles from readily available anti-3-aryl-2,3-di- was reduced to 90 °C, even after twenty-four hours
(Table 1, entry 11). In addition, adding more equivalents
of copper(I) iodide and sodium ascorbate appeared to be
unnecessary, whereas reducing the quantities of copper(I)
iodide and sodium ascorbate lowered the yield (Table 1,
SYNTHESIS 2010, No. 24, pp 4256–4260
Advanced online publication: 22.10.2010
DOI: 10.1055/s-0030-1258312; Art ID: F15610SS
© Georg Thieme Verlag Stuttgart · New York
x
x.
x
x
.
2
0
1
0

PAPER
4-Aryl-1H-1,2,3-triazoles
4257
entries 12–13). The reaction proceeded most efficiently methyl, or methoxycarbonyl (Table 2, entries 4–13).
and was complete in four hours when it was promoted by Moreover, the reaction of the pyridyl-substituted substrate
copper(I) iodide (10%) and sodium ascorbate (20%) in the also proceeded smoothly, giving an excellent yield of
presence of 2.5 equivalents of cesium carbonate as the 95% (Table 2, entry 14). Substrates bearing an electron-
base in dimethyl sulfoxide at 110 °C (Table 1, entry 8).
donating or an electron-withdrawing group at either the
para- or the meta-position gave the corresponding 4-aryl-
1H-1,2,3-triazoles in good-to-excellent yields (Table 2,
entries 2–11). Although the anti-3-aryl-2,3-dibromopro-
panoic acids bearing ortho-substituents gave lower yields,
the reactions also proceeded to completion within four
hours (Table 2, entries 11–13). It is obvious that electron-
withdrawing groups at either the para- or the meta- posi-
tion of the substrates are favored for this method, and
higher yields were achieved in these cases (Table 2, en-
tries 4–10).
Table 1 Optimization of the Conditions for the Conversion of Acid
1a into Triazole 2a
N
Br
N
NH
CuI, Na ascorbate, base
solvent, N2, 110 °C
CO2H
+ NaN3
Br
1a
2a
Entrya
1
Solvent
toluene
dioxane
DMF
Base
Time (h) Yield (%)b
K2CO3
K2CO3
K2CO3
Cs2CO3
K2CO3
K3PO4
KHCO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
24
12
8
18
32
56
60
65
40
38
76
68
0
Table 2 Copper(I) Iodide Catalyzed Synthesis of 4-Aryl-1H-1,2,3-
triazoles from anti-3-Aryl-2,3-dibromopropanoic Acids and Sodium
Azide
2
3
Br
N
4
DMF
6
N
CuI, Na ascorbate, Cs2CO3
DMSO, N2, 110 °C
CO2H
NH
+ NaN3
Ar
5
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
6
Ar
Br
1
2
6
8
Entrya
1
Product
Yield (%)b
7
10
4
N
N
8
NH
2a
76
9c
4
10d
11e
12f
13g
4
N
N
24
4
trace
70
55
NH
2
3
2b
2c
68
62
10
N
N
NH
a Unless otherwise noted, the reaction conditions were as follows: 1a
(0.5 mmol), NaN3 (1.3 equiv), base (2.5 equiv), CuI (10%), Na ascor-
bate (20%), solvent (3 mL), 110 °C, N2 atmosphere.
b Isolated yields based on 1a.
c The reaction was conducted in the absence of Na ascorbate.
d The reaction was conducted in the absence of both CuI and Na ascor-
bate.
N
N
NH
4
5
6
7
2d
2e
2f
76
83
86
88
e The reaction was conducted at 90 °C.
f 20% CuI and 40% Na ascorbate were used.
g 5% CuI and 10% Na ascorbate were used.
Br
Cl
F
N
N
NH
Having identified the optimal conditions, we examined
the substrate scope of this copper(I) iodide catalyzed syn-
thesis of 4-aryl-1H-1,2,3-triazoles, and we found that
these conditions appeared to be general for a broad spec-
trum of anti-3-aryl-2,3-dibromopropanoic acids (Table 2).
The starting anti-3-aryl-2,3-dibromopropanoic acids were
readily prepared by bromination of the corresponding
trans-a,b-unsaturated carboxylic acids.17 The results sum-
marized in Table 2 show that the present method can be
used for the synthesis of 4-aryl-1H-1,2,3-triazoles carry-
ing either an electron-donating substituent, such as methyl
or isopropyl (Table 2, entries 2–3), or an electron-with-
drawing group, such as bromo, chloro, fluoro, trifluoro-
N
N
NH
N
N
NH
2g
F3C
Synthesis 2010, No. 24, 4256–4260 © Thieme Stuttgart · New York

4258
Y. Jiang et al.
PAPER
Table 2 Copper(I) Iodide Catalyzed Synthesis of 4-Aryl-1H-1,2,3-
triazoles from anti-3-Aryl-2,3-dibromopropanoic Acids and Sodium
Azide (continued)
In summary, we have developed a simple and efficient
method for the preparation of 4-aryl-1H-1,2,3-triazoles 2
from anti-3-aryl-2,3-dibromopropanoic acids 1 and sodi-
um azide that is catalyzed by inexpensive copper(I) io-
dide. The products are obtained in moderate-to-excellent
yields, and the reaction provides a novel access to com-
pounds that are important in medicinal, materials, and
biological research.
Br
N
N
CuI, Na ascorbate, Cs2CO3
DMSO, N2, 110 °C
CO2H
NH
+ NaN3
Ar
Ar
Br
1
2
Entrya
8
Product
Yield (%)b
1H NMR spectra were recorded in DMSO-d6 or CDCl3 with TMS as
N
N
the internal standard by using a Bruker AM-500 spectrometer. 13
C
NH
2h
78
NMR spectra were recorded in CDCl3 by using a Bruker AM-500
spectrometer. Mass spectra were recorded on a Varian-310 mass
spectrometer. Commercially obtained reagents were used without
further purification. All reactions were conducted under N2 and
monitored by TLC on HuanghaiGF 254 silica gel coated plates.
Column chromatography was carried out on 300–400 mesh silica
gel at medium pressure. The anti-3-aryl-2,3-dibromopropanic acids
1 were synthesized according to literature procedures.17
MeO2C
N
N
N
N
N
N
NH
NH
NH
9
2i
2j
Br
Cl
74
82
4-Aryl-1H-1,2,3-triazoles 2: General Procedure
10
A soln of anti-3-aryl-2,3-dibromopropanic acid 1 (0.5 mmol), NaN3
(42 mg, 0.65 mmol), Cs2CO3 (408 mg, 1.25 mmol), CuI (10 mg,
0.05 mmol), and Na ascorbate (20 mg, 0.1 mmol) in DMSO (3 mL)
was stirred in a sealed tube under N2 for 5 min and then heated at
110 °C for 4 h. The mixture was allowed to cool to r.t. and then the
reaction was quenched with H2O (25 mL). The mixture was extract-
ed with EtOAc (3 × 30 mL), and the combined organic layers were
washed with brine (3 × 10 mL), dried (Na2SO4), and concentrated
under reduced pressure. The crude product was purified by column
chromatography [silica gel, EtOAc–hexane (1:10 to 1:2)].
Cl
11
2k
66
Cl
N
N
Cl
F
NH
NH
NH
12
13
2l
52
60
4-Phenyl-1H-1,2,3-triazole (2a)
1H NMR (500 MHz, CDCl3): d = 7.99 (s, 1 H), 7.83 (d, J = 7.1 Hz,
2 H), 7.48–7.45 (m, 2 H), 7.40–7.37 (m, 1 H).16
N
N
N
N
2m
4-(4-Tolyl)-1H-1,2,3-triazole (2b)
1H NMR (500 MHz, CDCl3): d = 7.95 (s, 1 H), 7.71 (d, J = 7.6 Hz,
2 H), 7.27 (d, J = 7.6 Hz, 2 H), 2.40 (s, 3 H).16
14
2n
95
4-(4-Isopropylphenyl)-1H-1,2,3-triazole (2c)
1H NMR (500 MHz, CDCl3): d = 7.94 (s, 1 H), 7.74 (d, J = 8.2 Hz,
2 H), 7.32 (d, J = 8.2 Hz, 2 H), 2.98–2.93 (m, 1 H), 1.29 (d, J = 6.9
Hz, 6 H).
13C NMR (125 MHz, CDCl3): d = 149.7, 146.9, 129.2, 127.1, 126.2,
126.1, 34.0, 23.8.
N
a The reaction conditions were as follows: substrate 1 (0.5 mmol),
NaN3 (0.65 mmol), Cs2CO3 (1.25 mmol), CuI (0.05 mmol), Na ascor-
bate (0.1 mmol), DMSO (3 mL), 110 °C, 4 h, N2 atmosphere.
b Isolated yield based on substrate 1.
ESI-MS: m/z (%) = 187 (100) [M+].
HRMS (ESI): m/z [M]+ calcd for C11H13N3: 187.1111; found:
187.1110.
To study the mechanism, we examined the reactions of 1-
ethynyl-4-methylbenzene, 1-[(Z)-(2-bromovinyl]-4-meth-
ylbenzene, and 1-[(E)-(2-bromovinyl]-4-methylbenzene
under the optimized conditions. 1-Ethynyl-4-methylben-
zene and 1-[(Z)-(2-bromovinyl]-4-methylbenzene gave
isolated yields of 76% and 70%, respectively, whereas no
product was observed in the case of 1-[(E)-(2-bromovi-
nyl]-4-methylbenzene. This suggests that an aralkyne is
generated in situ by debrominative decarboxylation of the
anti-3-aryl-2,3-dibromopropanoic acid 1 with subse-
quently elimination of hydrogen bromide. The aralkyne
then undergoes copper-catalyzed [3+2] cycloaddition
with the azide to give the corresponding 4-aryl-1H-1,2,3-
triazole 2.
4-(4-Bromophenyl)-1H-1,2,3-triazole (2d)
1H NMR (500 MHz, CDCl3): d = 7.96 (s, 1 H), 7.70 (d, J = 8.6 Hz,
2 H), 7.59 (d, J = 8.6 Hz, 2 H).16
4-(4-Chlorophenyl)-1H-1,2,3-triazole (2e)
1H NMR (500 MHz, CDCl3–DMSO-d6): d = 7.89 (s, 1 H), 7.76 (d,
J = 8.4 Hz, 2 H), 7.40 (d, J = 8.4 Hz, 2 H).16
4-(4-Fluorophenyl)-1H-1,2,3-triazole (2f)
1H NMR (500 MHz, CDCl3–DMSO-d6): d = 7.86 (s, 1 H), 7.82–
7.79 (m, 2 H), 7.14–7.10 (m, 2 H).16
Synthesis 2010, No. 24, 4256–4260 © Thieme Stuttgart · New York

PAPER
4-Aryl-1H-1,2,3-triazoles
4259
4-[4-(Trifluoromethyl)phenyl]-1H-1,2,3-triazole (2g)
1H NMR (500 MHz, CDCl3–DMSO-d6): d = 8.01–7.94 (m, 3 H),
7.69 (d, J = 8.2 Hz, 2 H).18
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1H NMR (500 MHz, CDCl3–DMSO-d6): d = 7.87 (s, 1 H), 7.77 (s,
1 H), 7.64 (s, 1 H), 7.32–7.29 (m, 1 H), 7.23 (d, J = 7.2 Hz, 1 H).20
4-(2,4-Dichlorophenyl)-1H-1,2,3-triazole (2k)
1H NMR (500 MHz, CDCl3–DMSO-d6): d = 8.19 (s, 1 H), 7.92 (br
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3-(1H-1,2,3-Triazol-4-yl)pyridine (2n)
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The work was supported by the Natural Science Foundation of Chi-
na (No. 30873153), the Key Projects of Shanghai in Biomedical
(No. 08431902700), and the Scientific Research Foundation of the
State Education Ministry for Returned Overseas Chinese Scholars.
We would like to thank the Center for Instrumental Analysis, Tongji
University, China.
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