Synthesis of arylseleno-1,2,3-triazoles via copper-catalyzed 1,3-dipolar cycloaddition of azido arylselenides with alkynes

Article abstract of DOI:10.1055/s-0030-1260083

The use of organoselenium compounds in the copper-catalyzed Huisgen 1,3-dipolar cycloaddition of azido arylselenides with various alkynes is described. Arylseleno-1,2,3-triazoles are prepared in excellent yields via reaction of amino arylselenides with is

Full text of DOI:10.1055/s-0030-1260083

PAPER
2397
Synthesis of Arylseleno-1,2,3-triazoles via Copper-Catalyzed 1,3-Dipolar
Cycloaddition of Azido Arylselenides with Alkynes
Synthesis of
Aryls
n
eleno-1,2, 3-t
n
riazoles a M. Deobald,a Leandro R. S. Camargo,a Manfredo Hörner,a Oscar E. D. Rodrigues,a Diego Alves,*b
Antonio L. Braga*c
a
Universidade Federal de Santa Maria, Departamento de Química, CEP 97105-900, Camobi, Santa Maria, RS, Brazil
LASOL, Universidade Federal de Pelotas, Departamento de Química Orgânica, CEP 96010-900, Pelotas, RS, Brazil
b
Fax +55(48)37216850; E-mail: diego.alves@ufpel.edu.br
Universidade Federal de Santa Catarina, Departamento de Química, CEP 88040-900, Florianópolis, SC, Brazil
c
E-mail: albraga@qmc.ufsc.br
Received 3 April 2011; revised 30 April 2011
protocol.3 The development of this copper-catalyzed pro-
cess represented an important advance in triazole synthe-
sis, and has become a paradigm of click chemistry.4 The
term click chemistry defines a chemical reaction which is
Abstract: The use of organoselenium compounds in the copper-
catalyzed Huisgen 1,3-dipolar cycloaddition of azido arylselenides
with various alkynes is described. Arylseleno-1,2,3-triazoles are
prepared in excellent yields via reaction of amino arylselenides with
iso-pentylnitrite and trimethylsilyl azide, and subsequent copper- versatile and clean, and which involves simple work-up
and purification procedures.4 The copper-catalyzed
catalyzed 1,3-dipolar cycloaddition of the resulting azido arylse-
lenides with alkynes. The cycloaddition is also performed under
azide–alkyne cycloaddition represents a very effective ex-
mild conditions with several azido arylselenides and phenylacety-
ample of click chemistry and has wide applications in var-
lene to afford the corresponding arylseleno-1,2,3-triazoles in good
ious fields of chemistry, such as in the discovery and
to excellent yields. This click chemistry protocol represents an effi-
modulation of drug candidates,5 the development of new
cient method to produce new selenium–nitrogen compounds.
materials,6 the design of new catalysts,7 supramolecular
Key words: organoselenium compounds, azides, click chemistry,
1,2,3-triazoles
chemistry8 and in biotechnology.9
Organoselenium compounds are attractive synthetic tar-
gets because of their chemo-, regio-, and stereoselective
reactions,10 and their association with biological activi-
1,2,3-Triazoles, which are five-membered nitrogen-con-
ties.11 Selenides or diselenides containing nitrogen atoms
taining heterocycles, are an important class of compounds
are a special class of these compounds which have been
employed in various organic transformations, for exam-
ple, in asymmetric synthesis.10d,12 Consequently, the
search for new and efficient methods for the preparation
of highly-functionalized organoselenium compounds re-
mains a challenge in organic chemistry. In a previous
communication, we described the synthesis of azido aryl-
selenides 1 starting from nitrogen-substituted benzenes to
afford the corresponding products in good to excellent
which display a wide spectrum of biological activity and
are employed extensively as explosives and agrochemi-
cals.1 There are several methods available in the literature
for the synthesis of 1,2,3-triazoles. One of the most attrac-
tive involves the thermal 1,3-dipolar cycloaddition of
azides with alkynes, as pioneered by Huisgen.2 The
Huisgen 1,3-dipolar cycloaddition route toward the syn-
thesis of 1,2,3-triazoles was popularized by Sharpless and
co-workers, who discovered a copper-catalyzed reaction
1) RSeSeR
NaBH4, EtOH
SeR
NH2
Cl
DMSO
2) Zn, NH4Cl
NO2
THF
40–84%
SeR
N3
1) i-C5H11ONO
THF, 0 °C
2) TMSN3
0 °C
1 h
r.t.
1
1) n-BuLi, THF
–78 °C, 1 h
]
R = aryl,
2
2) Y0, r.t., 1 h
I
Y
Y
3) K3Fe(CN)6 (aq)
NH2
NH2
NH2
Y = Se: 88%
Y = Te: 50%
Scheme 1 Syntheses of azido arylselenides and diselenides
SYNTHESIS 2011, No. 15, pp 2397–2406
x
x.
x
x
.
2
0
1
1
Advanced online publication: 21.06.2011
DOI: 10.1055/s-0030-1260083; Art ID: M35611SS
© Georg Thieme Verlag Stuttgart · New York

2398
A. M. Deobald et al.
PAPER
SeR1
SeR1
NH2
SeR1
N3
N
N
1) i-C5H11ONO
THF, 0 °C
copper salt
solvent
N
R2
R3
2) TMSN3
R3
0 °C
1 h
r.t.
R2
2
1
R1 = aryl,
]
3
2
R2 = aryl, alkyl, vinyl
R
3 = H, I
Scheme 2 Synthesis of arylseleno-1,2,3-triazoles 3
yields under mild reaction conditions (Scheme 1).13 This (CuSO4·5H2O) with sodium ascorbate in aqueous medi-
class of compounds has wider synthetic importance since um.3a Thus, in a preliminary set of experiments, we stud-
they combine the well-known reactivity of the azido ied the reaction of 2-azido arylselenide 1a with
group14 with that of a selenium-containing moiety.15
phenylacetylene (2a) in the presence of copper(II) sulfate
pentahydrate (5 mol%) and sodium ascorbate (10 mol%)
in mixtures of different solvents (Table 2).
Azido arylselenides 1 appear to be highly promising sub-
strates for copper-catalyzed 1,3-dipolar cycloadditions to
give selenium–triazole derivatives. Although the synthe- Analysis of the results in Table 2 revealed that the cy-
sis of selenium-containing triazole compounds has been cloaddition reaction afforded the desired product in high
reported previously,16 no procedure using a copper-cata- yields using a variety of solvent systems (Table 2, entries
lyzed protocol has been described so far. This fact encour- 1–6). An interesting feature of this method was that water
aged us to explore in detail the synthesis of azido was required as a co-solvent for successful 1,2,3-triazole
arylselenides and diselenides 1, and their subsequent use synthesis. This may be due to the increased solubility of
in the copper-catalyzed 1,3-dipolar cycloaddition with sodium ascorbate and the copper salt in this solvent. Re-
alkynes 2 to give arylseleno-1,2,3-triazoles 3 (Scheme 2). actions using ultrasonic irradiation and ionic liquids
proved to be less effective (Table 2, entries 9–11). Al-
though most of the solvent systems investigated led to for-
mation of the desired compound in high yield, the water–
Our initial studies were focused on the synthesis of azido
arylselenides and diselenides 1, as key intermediates for
the preparation of the desired arylseleno-1,2,3-triazoles.
tetrahydrofuran (1:1) mixture proved to be the most effec-
Starting from nitrogen-substituted benzenes, and follow-
tive for this transformation (Table 2, entry 6). It is impor-
ing incorporation of the arylselenium moiety on the aro-
matic ring, a number of amino arylselenides were
tant to note that the reaction was not air-sensitive.
obtained with satisfactory results (Scheme 1).13 These The influence of the type and amount of copper salt on this
compounds were converted into azido arylselenides 1 in reaction was also studied. Various copper catalysts in-
good to excellent yields after reaction with iso-pentylni- cluding copper(II) sulfate pentahydrate, copper(II) bro-
trite and trimethylsilyl azide in tetrahydrofuran at 0 °C. mide, copper(II) triflate [Cu(OTf)2], copper(II) acetate
Using optimized reaction conditions the corresponding monohydrate [Cu(OAc)2·H2O] and copper(II) oxide nano-
azido arylchalcogenides and dichalcogenides were syn- particles (CuO NPs) were tested, and found to display
thesized and the results are summarized in Table 1.
moderate to good catalytic activity (Table 3). Of the cop-
per salts examined, copper(II) acetate monohydrate (5
mol%) gave the highest catalytic activity, affording com-
pound 3a in 92% yield (Table 3, entry 5). Good yields of
product 3a were also obtained when the amount of the
copper catalyst was reduced (2.5 mol% and 1 mol%)
(Table 3, entries 7 and 8). The reaction time had an influ-
ence on the yield of product 3a, and the best yield (97%)
was obtained after 12 hours at room temperature using 1
mol% of catalyst (Table 3, entry 10).
Analysis of these results indicated that the reactions were
slightly sensitive to electronic effects. Examples with
electron-neutral and electron-donating groups on the ar-
ylseleno moiety gave the best yields of products (Table 1,
entries 1–3, 5 and 6). The presence of electron-withdraw-
ing groups on the arylseleno moiety led to decreased
yields of the desired products (Table 1, entries 4 and 7).
Compound 1h, a hindered azido arylselenide, was ob-
tained in 75% yield (Table 1, entry 8). This method was
extended to other amino arylchalcogenide and dichalco- Under the optimized conditions, a variety of terminal
genides to give azido arylsulfide 1j, azido aryldiselenide alkynes reacted smoothly with 2-azido arylselenide 1a to
1k and azido arylditelluride 1l in 99%, 71% and 50% produce arylseleno-1,2,3-triazoles 3a–n in good to excel-
yields, respectively (Table 1, entries 10–12).
lent yields (Table 4). Alkynes possessing phenyl, substi-
tuted aryl, alkyl, vinyl and ester groups were tolerated in
this 1,3-dipolar cycloaddition reaction, as were those with
hydroxy and amine functional groups (Table 4, entries 1–
12). Interesting results were obtained using (iodoeth-
ynyl)benzene and tetradeca-1,13-diyne. These alkynes
Next, we turned our attention to the application of azido
arylselenides 1 for the synthesis of arylseleno-1,2,3-triaz-
oles 3, using a copper-catalyzed 1,3-dipolar cycloaddition
protocol. The most common experimental procedure for
this reaction involves the in situ generation of a copper(I)
species by reduction of copper(II) sulfate pentahydrate
Synthesis 2011, No. 15, 2397–2406 © Thieme Stuttgart · New York

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Synthesis of Arylseleno-1,2,3-triazoles
2399
Table 1 Synthesis of Azido Arylchalcogenides 1a–l
Table 2 A Study of the Effect of Solvent on the Cycloaddition of 2-
Azido Arylselenide 1a and Phenylacetylene (2a)
1) i-C5H11ONO
SeAr
SeAr
THF, 0 °C
SePh
2) TMSN3
0 °C
1 h
NH2
N3
1a–l
r.t.
SePh
N3
CuSO4•5H2O (5 mol%)
1a
sodium ascorbate (10 mol%)
N
Entry
1
Product
Yield (%)a
99
N
+
N
solvent
r.t., air, 6 h
Ph
H
2a
3a
Ph
1a
1b
1c
Yield of 3a (%)a
Se
Se
Entry
Solvent (ratio)
N3
1
2
H2O–MeOH (1:1)
H2O–MeOH (0.5:1)
H2O–CH2Cl2 (1:1)
H2O–Et2O (1:1)
H2O–acetone (1:1)
H2O–THF (1:1)
H2O–THF (0.5:1)
H2O–THF (1:1)b
H2O–THF (1:1)c
85
83
81
86
87
89
47
87
68
–
2
3
96
95
3
N3
OMe
Cl
4
5
Se
N3
6
7
4
5
6
7
1d
1e
1f
88
99
95
80
8
Se
Se
Se
N3
N3
N3
9
d
10
11
[bmim]BF4
H2O–[bmim]BF4 (1:1)
56
a Yield of isolated product.
b Reaction under an Ar atmosphere.
c Reaction under ultrasonic irradiation for 2 h.
d [bmim]BF4 = 1-butyl-3-methylimidazolium tetrafluoroborate.
OMe
Cl
were cyclized efficiently to afford triazoles 3m and 3n in
1g
good yields (Table 4, entries 13 and 14).
Se
Se
To further extend the scope of this reaction, phenylacety-
lene (2a) was reacted with several azido arylselenides and
the results are summarized in Table 5. 2-Azido arylse-
lenides bearing electron-donating and electron-withdraw-
ing groups on the arylselenium moiety produced the
corresponding arylseleno-1,2,3-triazoles 3o–t in good to
excellent yields (Table 5, entries 1–6). Additionally, the
use of a 4-azido arylselenide gave the desired product 3v
in 65% yield (Table 5, entry 8). The synthesis of triazoles
using other 1-azido arylchalcogenides was studied next.
When 2-azido arylsulfide was used, triazole 3w was ob-
tained in an excellent 99% yield (Table 5, entry 9). Nota-
bly, when azido aryldiselenide 1k was used as the
substrate, a satisfactory yield of diaryl-diseleno-1,2,3-tri-
azole 3x was obtained (Table 5, entry 10). These dise-
lenide-1,2,3-triazoles have greater synthetic importance
since they combine the well-known activity of the triazole
group1 with that of a diselenide moiety.11 Extending this
protocol to azido-tellurium analogue 1l, we synthesized
diaryl-ditelluro-1,2,3-triazole 3y in 63% yield (Table 5,
entry 11). Interestingly, these results show that the Se–Se
and Te–Te bonds were not affected in this copper-cata-
lyzed azide–alkyne cycloaddition; a similar situation was
described by Theato and co-workers for S–S bonds.17
N3
8
9
1h
1i
75
75
99
N3
N3
Se
10
1j
S
N3
N3
N3
11
12
1k
1l
71
50
Se Se
Te Te
N3
N3
a Yield of isolated product.
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A. M. Deobald et al.
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Table 4 Reaction of 1a with Various Alkynes (continued)
Table 3 The Effect of Various Copper Salts on the Cycloaddition of
2-Azido Arylselenide 1a and Phenylacetylene (2a)
SePh
SePh
SePh
N3
Cu(OAc)2•H2O (1 mol%)
sodium ascorbate (2 mol%)
SePh
1a
N3
N
N
copper salt
1a
+
N
sodium ascorbate
N
H2O–THF (1:1)
r.t., 12 h
N
R1
R2
+
N
R2
3a–n
H2O–THF (1:1)
r.t., air, 6 h
2a–n
R1
Ph
H
2a
3a
Ph
Entry
Product
Yield
(%)a
Entry
Copper salt
(mol%)
Sodium ascorbate Yield of 3a
(mol%)
(%)a
89
71
66
77
92
93
90
89
20
97
1
2
CuSO4·5H2O (5)
CuBr2 (5)
10
10
10
10
10
10
5
SePh
N
N
3
Cu(OTf)2 (5)
3
3c (94%)
94
N
4
CuO NPs (5)
5
Cu(OAc)2·H2O (5)
Cu(OAc)2·H2O (5)b
Cu(OAc)2·H2O (2.5)
Cu(OAc)2·H2O (1)
Cu(OAc)2·H2O (0.5)
Cu(OAc)2·H2O (1)c
Cl
6
7
SePh
8
2
4
5
3d (85%)
3e (95%)
85
95
N
N
N
N
9
1
N
C4H9
10
2
a Yield of isolated product.
b Reaction at 50 °C.
c Reaction was performed for 12 h at r.t.
SePh
N
Table 4 Reaction of 1a with Various Alkynes
N
SePh
C8H17
SePh
N3
Cu(OAc)2•H2O (1 mol%)
sodium ascorbate (2 mol%)
1a
SePh
N
N
+
6
7
8
3f (87%)
3g (90%)
3h (91%)
87
90
91
N
H2O–THF (1:1)
R1
R2
N
r.t., 12 h
R2
3a–n
2a–n
R1
N
Entry
Product
Yield
(%)a
SePh
N
N
SePh
1
3a (97%)
97
N
N
N
OH
N
Ph
SePh
SePh
N
N
N
2
3b (96%)
N
96
N
N
OH
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Synthesis of Arylseleno-1,2,3-triazoles
2401
Table 5 Reaction of Phenylacetylene (2a) with Various Azido
Arylselenides
Table 4 Reaction of 1a with Various Alkynes (continued)
SePh
YR
SePh
N3
YR
Cu(OAc)2•H2O (1 mol%)
N3
1a
sodium ascorbate (2 mol%)
Cu(OAc)2•H2O (1 mol%)
N
1b–l
N
+
sodium ascorbate (2 mol%)
N
N
N
H2O–THF (1:1)
r.t., 12 h
+
N
R1
R2
H2O–THF (1:1)
r.t., 12 h
R2
3a–n
Ph
H
2a–n
R1
2a
Ph
3o–y
Entry
Product
Yield
(%)a
Entry
1
Product
Yield (%)a
Se
SePh
N
3o
3p
98
N
N
9
3i (97%)
97
N
N
N
OH
Ph
OMe
Se
2
94
N
N
SePh
N
10
11
3j (75%)
75
87
N
Ph
N
Cl
N
13OH
SePh
O
Se
3
4
5
6
7
3q
3r
3s
3t
88
90
91
87
75
N
N
N
N
N
N
N
3k (87%)
N
Ph
N
N
Se
MeO
N
N
SePh
Ph
12
3l (86%)
N
86
N
N
Se
OMe
NH2
N
N
Ph
SePh
I
13
14
3m (83%)
3n (92%)
83
92
N
N
Se
N
Cl
Ph
N
SePh
N
Ph
N
PhSe
N
N
Se
N
N
3u
N
N
N
a Yield of isolated product.
Ph
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A. M. Deobald et al.
PAPER
Table 5 Reaction of Phenylacetylene (2a) with Various Azido Ar-
ylselenides (continued)
In summary, we have described the use of organoseleni-
um compounds in copper-catalyzed Huisgen 1,3-dipolar
cycloadditions. Arylseleno-1,2,3-triazoles 3 were pre-
pared in good to excellent yields under mild conditions
via reaction of amino arylselenides with iso-pentylnitrite
and trimethylsilyl azide, and subsequent copper-catalyzed
1,3-dipolar cycloaddition of the resulting azido arylse-
lenides 1 with various alkynes. In addition, we were able
to convert compound 3m into highly-substituted 1,2,3-tri-
azole 4 in good yield using the Suzuki cross-coupling pro-
tocol. We have demonstrated that click chemistry is an
efficient method to produce new selenium–nitrogen com-
pounds with potential application for biological studies
and as ligands for catalytic transformations.
YR
YR
N3
Cu(OAc)2•H2O (1 mol%)
sodium ascorbate (2 mol%)
1b–l
N
N
+
N
H2O–THF (1:1)
r.t., 12 h
Ph
H
2a
Ph
3o–y
Entry
Product
Yield (%)a
N
Ph
N
N
8
3v
65
All solvents were used as purchased unless otherwise noted.
Alkynes were used as purchased or were prepared according to the
literature.19 Melting points were determined on an MQ APF–302
Se
1
digital melting point apparatus. H and 13C NMR spectra were re-
corded at 400 MHz and 100 MHz, respectively, using Me4Si as the
internal standard. Hydrogen coupling patterns are described as sin-
glet (s), doublet (d), triplet (t), quartet (q), quintet (quin), sextet
(sext), multiplet (m), and broad (br). High resolution mass spectra
were measured using a Bruker BioApex 70e FT-ICR (Bruker Dal-
tonics, Billerica, USA) instrument in ESI mode. Column chroma-
tography was performed using silica gel (Merck, 230–400 mesh).
Thin layer chromatography (TLC) was performed using silica gel
plates (Merck GF254, 0.25 mm). For visualization, TLC plates were
either placed under UV light, or stained with I2 vapor, or acidic van-
illin.
S
9
10
11
3w
3x
3y
99
60
63
N
N
N
N
N
Ph
Se
2
N
N
Azido Arylselenides; General Procedure
Ph
iso-Pentylnitrite (1.55 mmol, 0.21 mL) followed by trimethylsilyl
azide (1.2 mmol, 0.16 mL) were added to a soln of amino arylse-
lenide (1 mmol) or amino aryldiselenide (0.5 mmol) in THF (1.5
mL), in a dropwise manner at 0 °C under air. The mixture was
stirred at 0 °C for 10 min after which the ice-bath was removed and
the mixture stirred at r.t. for 1 h. The solvent was removed under
vacuum and the product was isolated by column chromatography
(eluent: hexane or hexane–EtOAc).
Te
2
N
N
Ph
a Yield of isolated product.
(2-Azidophenyl)(phenyl)selenide (1a)
Yield: 0.272 g (99%); yellow solid; mp 49–50 °C.
1H NMR (400 MHz, CDCl3): d = 7.56–7.53 (m, 2 H), 7.35–7.30 (m,
3 H), 7.23 (td, 1J = 8.0 Hz, 2J = 1.2 Hz, 1 H), 7.12 (dd, 1J = 8.0 Hz,
2J = 1.2 Hz, 1 H), 7.02 (dd, 1J = 8.0 Hz, 2J = 1.2 Hz, 1 H), 6.94 (td,
1J = 8.0 Hz, 2J = 1.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 138.83, 135.10, 131.86, 129.56,
128.30, 128.25, 127.88, 125.52, 124.57, 118.17.
Finally, compound 3m, obtained via this cycloaddition
protocol, proved to be promising as an intermediate in the
preparation of more highly-substituted 1,2,3-triazoles.
Triazole 3m underwent Suzuki cross-coupling18 with (4-
methoxyphenyl)boronic acid to give the corresponding
4,5-disubstituted arylseleno-1,2,3-triazole 4 in good yield
(Scheme 3).
(2-Azidophenyl)(p-tolyl)selenide (1b)
Yield: 0.276 g (96%); red oil.
1H NMR (400 MHz, CDCl3): d = 7.45 (d, J = 8.0 Hz, 2 H), 7.19–
7.06 (m, 4 H), 6.94–6.87 (m, 2 H), 2.34 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 138.61, 138.17, 135.75, 130.87,
130.39, 127.35, 125.42, 123.96, 119.55, 117.98, 21.15.
SePh
SePh
N
MeO
B(OH)2
N
N
N
N
N
Pd(OAc)2 (5%), K3PO4
DMF–H2O, reflux, 12 h
Ph
I
Ph
(2-Azidophenyl)(4-methoxyphenyl)selenide (1c)
Yield: 0.289 g (95%); pale-yellow solid; mp 63–64 °C.
3m
MeO
4 (78%)
1H NMR (400 MHz, CDCl3): d = 7.54 (d, J = 8.8 Hz, 2 H), 7.19 (td,
1J = 8.0 Hz, 2J = 1.6 Hz, 1 H), 7.10 (dd, 1J = 8.0 Hz, 2J = 1.6 Hz, 1
H), 6.93–6.89 (m, 3 H), 6.84 (dd, 1J = 8.0 Hz, 2J = 1.6 Hz, 1 H), 3.84
(s, 3 H).
Scheme 3 Suzuki cross-coupling of triazole 3m
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Synthesis of Arylseleno-1,2,3-triazoles
2403
13C NMR (100 MHz, CDCl3): d = 160.14, 137.92, 137.42, 129.77,
126.86, 126.17, 125.30, 117.77, 117.10, 115.18, 55.02.
1H NMR (400 MHz, DMSO-d6): d = 8.02 (dd, 1J = 8.0 Hz, 2J = 1.2
Hz, 2 H), 7.84–7.73 (m, 4 H), 7.60–7.56 (m, 2 H).
13C NMR (100 MHz, DMSO-d6): d = 148.93, 141.24, 139.27,
138.47, 136.21, 128.90.
(2-Azidophenyl)(4-chlorophenyl)selenide (1d)
Yield: 0.271 g (88%); yellow solid; mp 36–37 °C.
1H NMR (400 MHz, CDCl3): d = 7.45 (d, J = 8.4 Hz, 2 H), 7.29–
7.24 (m, 3 H), 7.14 (d, J = 7.6 Hz, 1 H), 7.05 (d, J = 7.6 Hz, 1 H),
6.96 (t, J = 7.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 136.20, 134.67, 132.19, 129.78,
129.44, 128.30, 126.77, 125.64, 123.96, 118.32.
1,2-Bis(2-azidophenyl)ditelluride (1l)
Yield: 0.124 g (50%); brown oil.
1H NMR (400 MHz, DMSO-d6): d = 8.64–8.62 (m, 2 H), 8.22–8.15
(m, 4 H), 8.03–7.99 (m, 2 H).
13C NMR (100 MHz, DMSO-d6): d = 138.51, 130.89, 129.13,
128.08, 123.98, 118.53.
(2-Azidophenyl)(o-tolyl)selenide (1e)
Yield: 0.285 g (99%); red oil.
Aryseleno-1,2,3-Triazoles; General Procedure
1H NMR (400 MHz, CDCl3): d = 7.48 (d, J = 8.0 Hz, 1 H), 7.31–
7.28 (m, 2 H), 7.25–7.21 (m, 1 H), 7.14–7.11 (m, 2 H), 6.92 (td,
1J = 8.0 Hz, 2J = 1.2 Hz, 1 H), 6.84 (dd, 1J = 8.0 Hz, 2J = 1.2 Hz, 1
H), 2.40 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 141.80, 138.82, 136.24, 131.12,
130.45, 129.00, 128.81, 127.63, 126.95, 125.58, 124.05, 118.19,
22.52.
To a soln of azido arylselenide (0.3 mmol) in THF (1.0 mL) were
added the appropriate alkyne (0.33 mmol) and distilled H2O (0.5
mL). Next, a fresh soln of sodium ascorbate (0.0012 g, 2 mol%) and
Cu(OAc)2·H2O (0.0006 g, 1 mol%) in distilled H2O (0.5 mL) was
added and the mixture stirred under air for 12 h. Brine (3 mL) was
added and the mixture then extracted with CH2Cl2 (3 × 5 mL). The
organic layers were combined, washed with brine (3 mL) and dried
over MgSO4. The solvent was removed under vacuum and the
product isolated by column chromatography (eluent: hexane–
EtOAc).
(2-Azidophenyl)(2-methoxyphenyl)selenide (1f)
Yield: 0.290 g (95%); pale-yellow solid; mp 58–60 °C.
1H NMR (400 MHz, CDCl3): d = 7.33–7.22 (m, 3 H), 7.17 (d,
J = 7.6 Hz, 1 H), 7.11 (d, J = 7.2 Hz, 1 H), 6.99 (t, J = 7.2 Hz, 1 H),
6.89 (d, J = 7.6 Hz, 1 H), 6.84 (t, J = 7.2 Hz, 1 H), 3.84 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 157.80, 140.74, 134.60, 133.24,
129.00, 128.87, 125.45, 121.61, 118.75, 118.33, 110.67, 99.98,
55.84.
4-Phenyl-1-[2-(phenylselanyl)phenyl]-1H-1,2,3-triazole (3a)
Yield: 0.110 g (97%); white solid; mp 149–150 °C.
1H NMR (400 MHz, CDCl3): d = 8.07 (s, 1 H), 7.91–7.89 (m, 2 H),
7.51–7.43 (m, 5 H), 7.38–7.27 (m, 7 H).
13C NMR (100 MHz, CDCl3): d = 147.67, 136.85, 135.02, 133.16,
130.25, 130.15, 130.12, 129.63, 128.84, 128.60, 128.29, 127.64,
126.05, 125.85, 120.96, 99.91.
(2-Azidophenyl)(2-chlorophenyl)selenide (1g)
Yield: 0.247 g (80%); pale-yellow oil.
HRMS: m/z calcd [M + H]+ for C20H16N3Se: 378.0509; found:
378.0506.
1H NMR (400 MHz, CDCl3): d = 7.42–7.38 (m, 2 H), 7.35 (dd,
1J = 8.0 Hz, 2J = 1.2 Hz, 1 H), 7.25–7.17 (m, 2 H), 7.12–7.05 (m, 3
1-[2-(Phenylselanyl)phenyl]-4-(p-tolyl)-1H-1,2,3-triazole (3b)
Yield: 0.113 g (96%); pale-yellow solid; mp 135–137 °C.
1H NMR (400 MHz, CDCl3): d = 8.03 (s, 1 H), 7.78 (d, J = 8.0 Hz,
2 H), 7.50–7.44 (m, 4 H), 7.36–7.24 (m, 7 H), 2.38 (s, 3 H).
H).
13C NMR (100 MHz, CDCl3): d = 141.51, 135.77, 135.31, 132.66,
131.09, 129.88, 129.68, 128.33, 127.42, 125.72, 120.77, 118.65.
(2-Azidophenyl)(mesityl)selenide (1h)
Yield: 0.238 g (75%); yellow solid; mp 88–90 °C.
13C NMR (100 MHz, CDCl3): d = 147.72, 138.12, 136.83, 135.03,
133.04, 130.09, 130.04, 129.59, 129.48, 128.81, 128.56, 127.55,
127.39, 125.95, 125.72, 120.56, 21.24.
HRMS: m/z calcd [M + Na]+ for C21H17N3SeNa: 414.0485; found:
414.0479.
1H NMR (400 MHz, CDCl3): d = 7.16–7.08 (m, 2 H), 7.02 (s, 2 H),
1
2
1
6.84 (td, J = 8.0 Hz, J = 1.6 Hz, 1 H), 6.47 (dd, J = 8.0 Hz,
2J = 1.6 Hz, 1 H), 2.41 (s, 6 H), 2.32 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 144.13, 139.54, 137.56, 128.99,
127.74, 126.28, 125.62, 125.37, 125.07, 118.00, 24.02, 21.05.
4-(4-Chlorophenyl)-1-[2-(phenylselanyl)phenyl]-1H-1,2,3-tria-
zole (3c)
Yield: 0.115 g (94%); pale-yellow solid; mp 165–167 °C.
1H NMR (400 MHz, CDCl3): d = 8.06 (s, 1 H), 7.83 (d, J = 8.8 Hz,
2 H), 7.49–7.46 (m, 4 H), 7.43–7.25 (m, 7 H).
13C NMR (100 MHz, CDCl3): d = 146.61, 136.78, 134.95, 134.06,
133.26, 130.28, 130.04, 129.66, 129.06, 128.79, 128.76, 128.63,
127.71, 127.09, 126.06, 121.05.
(4-Azidophenyl)(phenyl)selenide (1i)
Yield: 0.206 g (75%); orange oil.
1H NMR (400 MHz, CDCl3): d = 7.46–7.40 (m, 4 H), 7.26–7.24 (m,
3 H), 6.92 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 139.57, 134.92, 132.94, 132.49,
129.34, 127.30, 126.67, 119.95.
HRMS: m/z calcd [M + H]+ for C20H15ClN3Se: 412.0120; found:
(2-Azidophenyl)(phenyl)sulfide (1j)
412.0114.
Yield: 0.228 g (99%); colorless oil.
4-Butyl-1-[2-(phenylselanyl)phenyl]-1H-1,2,3-triazole (3d)
Yield: 0.091 g (85%); pale-yellow solid; mp 70–71 °C.
1H NMR (400 MHz, CDCl3): d = 7.61 (s, 1 H), 7.49–7.47 (m, 2 H),
7.41–7.39 (m, 1 H), 7.34–7.22 (m, 6 H), 2.81 (t, J = 7.2 Hz, 2 H),
1.73 (quin, J = 7.2 Hz, 2 H), 1.43 (sext, J = 7.2 Hz, 2 H), 0.96 (t,
J = 7.2 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.33–7.22 (m, 7 H), 7.14–7.08 (m,
1 H), 7.02–6.97 (m, 1 H).
13C NMR (100 MHz, CDCl3): d = 139.02, 133.77, 131.99, 131.55,
129.24, 128.16, 127.42, 127.21, 125.24, 118.56.
1,2-Bis(2-azidophenyl)diselenide (1k)
Yield: 0.141 g (71%); brown oil.
Synthesis 2011, No. 15, 2397–2406 © Thieme Stuttgart · New York

2404
A. M. Deobald et al.
PAPER
13C NMR (100 MHz, CDCl3): d = 148.19, 136.86, 134.94, 132.68,
129.96, 129.75, 129.48, 128.73, 128.44, 127.31, 125.80, 121.88,
31.29, 25.16, 22.15, 13.71.
13C NMR (100 MHz, CDCl3): d = 155.32, 136.92, 134.84, 133.06,
129.99, 129.93, 129.58, 128.82, 128.50, 127.56, 126.04, 121.19,
69.56, 38.06, 25.32, 21.98.
HRMS: m/z calcd [M + H]+ for C18H20N3Se: 358.0822; found:
HRMS: m/z calcd [M + Na]+ for C20H21N3OSeNa: 422.0748; found:
358.0816.
422.0742.
4-Octyl-1-[2-(phenylselanyl)phenyl]-1H-1,2,3-triazole (3e)
Yield: 0.117 g (95%); yellowish solid; mp 66–68 °C.
13-{1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}tridecan-
1-ol (3j)
Yield: 0.106 g (75%); white solid; mp 80–82 °C.
1H NMR (400 MHz, CDCl3): d = 7.61 (s, 1 H), 7.49–7.47 (m, 2 H),
7.40–7.38 (m, 1 H), 7.33–7.21 (m, 6 H), 2.79 (t, J = 7.2 Hz, 2 H),
1.74 (quin, J = 7.2 Hz, 2 H), 1.45–1.27 (m, 10 H), 0.87 (t, J = 7.2
Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 148.19, 136.84, 134.92, 132.63,
129.94, 129.70, 129.45, 128.71, 128.41, 127.27, 125.76, 121.85,
31.67, 29.16, 29.13, 29.07, 29.04, 25.46, 22.47, 13.93.
1H NMR (400 MHz, CDCl3): d = 7.61 (s, 1 H), 7.49–7.47 (m, 2 H),
7.41–7.39 (m, 1 H), 7.35–7.24 (m, 6 H), 3.62 (t, J = 7.6 Hz, 2 H),
2.79 (t, J = 7.6 Hz, 2 H), 2.24 (s, 1 H), 1.74 (quin, J = 7.6 Hz, 2 H),
1.56 (quin, J = 7.6 Hz, 2 H), 1.42–1.26 (m, 18 H).
13C NMR (100 MHz, CDCl3): d = 148.23, 136.84, 134.95, 132.69,
129.98, 129.78, 129.49, 128.71, 128.46, 127.32, 125.82, 121.94,
67.95, 62.67, 32.63, 29.45, 29.42, 29.38, 29.29, 29.21, 29.17, 29.07,
25.62, 25.45.
HRMS: m/z calcd [M + H]+ for C22H28N3Se: 414.1448; found:
414.1442.
HRMS: m/z calcd [M + H]+ for C27H38N3OSe: 500.2180; found:
1-[2-(Phenylselanyl)phenyl]-4-(prop-1-en-2-yl)-1H-1,2,3-tria-
zole (3f)
Yield: 0.089 g (87%); pale-yellow solid; mp 90–92 °C.
1H NMR (400 MHz, CDCl3): d = 7.79 (s, 1 H), 7.49–7.47 (m, 2 H),
7.42–7.39 (m, 1 H), 7.35–7.24 (m, 6 H), 5.82 (s, 1 H), 5.17–5.15 (m,
1 H), 2.17 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 148.53, 136.69, 134.94, 133.08,
132.95, 130.60, 130.01, 129.96, 129.53, 128.79, 127.50, 125.82,
120.86, 112.95, 20.55.
500.2174.
Methyl 1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazole-4-car-
boxylate (3k)
Yield: 0.094 g (87%); yellow solid; mp 81–82 °C.
1H NMR (400 MHz, CDCl3): d = 8.41 (s, 1 H), 7.46–7.26 (m, 9 H),
3.98 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 160.76, 139.56, 136.11, 134.52,
133.48, 130.65, 129.73, 129.53, 128.85, 128.52, 128.25, 127.85,
126.13, 52.07.
HRMS: m/z calcd [M + Na]+ for C17H15N3SeNa: 364.0329; found:
364.0323.
HRMS: m/z calcd [M + H]+ for C16H14N3O2Se: 360.0251; found:
360.0245.
2-{1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}butan-2-
ol (3g)
Yield: 0.101 g (90%); white solid; mp 131–133 °C.
2-{1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}propan-2-
amine (3l)
Yield: 0.092 g (86%); white solid; mp 82–83 °C.
1H NMR (400 MHz, CDCl3): d = 7.79 (s, 1 H), 7.48–7.46 (m, 2 H),
7.43–7.40 (m, 1 H), 7.33–7.25 (m, 6 H), 2.89 (br s, 1 H), 1.98 (q,
J = 7.6 Hz, 2 H), 1.66 (s, 3 H), 0.92 (t, J = 7.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 154.40, 136.79, 134.88, 132.89,
130.05, 129.98, 129.55, 128.72, 128.49, 127.45, 125.96, 121.42,
71.22, 35.83, 27.88, 8.27.
1H NMR (400 MHz, CDCl3): d = 7.84 (s, 1 H), 7.50–7.47 (m, 2 H),
7.42 (d, J = 7.6 Hz, 1 H), 7.35–7.26 (m, 6 H), 3.72 (s, 2 H), 2.33 (s,
6 H).
13C NMR (100 MHz, CDCl3): d = 144.87, 136.73, 134.92, 132.75,
130.09, 129.96, 129.52, 128.61, 128.48, 127.38, 125.86, 123.79,
54.13, 44.99.
HRMS: m/z calcd [M + H]+ for C18H20N3OSe: 374.0772; found:
374.0766.
HRMS: m/z calcd [M + Na]+ for C17H18N4SeNa: 381.0594; found:
381.0588.
2-{1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}ethanol
(3h)
Yield: 0.094 g (91%); beige solid; mp 82–84 °C.
5-Iodo-4-phenyl-1-[2-(phenylselanyl)phenyl]-1H-1,2,3-triazole
(3m)
Yield: 0.125 g (83%); yellow oil.
1H NMR (400 MHz, CDCl3): d = 8.08–8.06 (m, 2 H), 7.52–7.47 (m,
4 H), 7.43–7.34 (m, 5 H), 7.31–7.25 (m, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.76 (s, 1 H), 7.48–7.45 (m, 2 H),
7.39 (dd, 1J = 7.6 Hz, 2J = 1.2 Hz, 1 H), 7.33–7.22 (m, 6 H), 3.99 (t,
J = 6.0 Hz, 2 H), 3.14 (s, 1 H), 3.04 (t, J = 6.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 136.63, 134.92, 132.76, 129.97,
129.88, 129.50, 128.67, 128.48, 127.37, 125.77, 122.99, 61.28,
28.68.
13C NMR (100 MHz, CDCl3): d = 149.49, 136.77, 135.14, 133.48,
133.24, 131.23, 129.96, 129.51, 128.60, 128.57, 128.55, 128.49,
128.39, 127.61, 127.42.
HRMS: m/z calcd [M + H]+ for C16H16N3OSe: 346.0459; found:
HRMS: m/z calcd [M + H]+ for C20H15IN3Se: 503.9476; found:
346.0453.
503.9470.
1-{1-[2-(Phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}cyclohex-
anol (3i)
Yield: 0.116 g (97%); white solid; mp 154–156 °C.
1,10-Bis{1-[2-(phenylselanyl)phenyl]-1H-1,2,3-triazol-4-yl}de-
cane (3n)
Yield: 0.204 g (92%); white solid; mp 143–144 °C.
1H NMR (400 MHz, CDCl3): d = 7.79 (s, 1 H), 7.47–7.41 (m, 3 H),
7.35–7.25 (m, 6 H), 2.81 (s, 1 H), 2.10–2.04 (m, 2 H), 1.97–1.93 (m,
2 H), 1.83–1.74 (m, 2 H), 1.66–1.55 (m, 3 H), 1.45–1.38 (m, 1 H).
1H NMR (400 MHz, CDCl3): d = 7.58 (s, 2 H), 7.48–7.46 (m, 4 H),
7.41 (d, J = 7.6 Hz, 2 H), 7.34–7.22 (m, 12 H), 2.79 (t, J = 7.2 Hz,
4 H), 1.74 (quin, J = 7.2 Hz, 4 H), 1.41–1.25 (m, 12 H).
Synthesis 2011, No. 15, 2397–2406 © Thieme Stuttgart · New York

PAPER
Synthesis of Arylseleno-1,2,3-triazoles
2405
13C NMR (100 MHz, CDCl3): d = 148.32, 137.33, 134.95, 133.10,
130.03, 129.83, 129.58, 129.08, 128.49, 127.51, 126.08, 122.01,
29.46, 29.31, 29.29, 29.18, 25.62.
1-{2-[(2-Chlorophenyl)selanyl]phenyl}-4-phenyl-1H-1,2,3-tria-
zole (3t)
Yield: 0.107 g (87%); yellow oil.
HRMS: m/z calcd [M + H]+ for C38H41N6Se2: 741.1723; found:
741.1717.
1H NMR (400 MHz, CDCl3): d = 8.10 (s, 1 H), 7.87–7.83 (m, 2 H),
1
2
1
7.55 (dd, J = 8.0 Hz, J = 1.6 Hz, 1 H), 7.50 (dd, J = 7.6 Hz,
2J = 1.2 Hz, 1 H), 7.45–7.32 (m, 4 H), 7.26–7.23 (m, 2 H), 7.20 (dt,
1J = 8.0 Hz, 2J = 1.6 Hz, 1 H), 7.16 (dd, 1J = 7.6 Hz, 2J = 1.2 Hz, 1
H), 7.06 (dd, 1J = 7.6 Hz, 2J = 1.2 Hz, 1 H).
4-Phenyl-1-[2-(p-tolylselanyl)phenyl]-1H-1,2,3-triazole (3o)
Yield: 0.105 g (98%); pale-yellow solid; mp 107–108 °C.
1H NMR (400 MHz, CDCl3): d = 8.07 (s, 1 H), 7.90 (d, J = 8.0 Hz,
2 H), 7.44–7.22 (m, 9 H), 7.09 (d, J = 8.0 Hz, 2 H), 2.31 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 138.87, 136.29, 135.48, 132.25,
130.71, 130.40, 129.95, 128.76, 128.72, 128.16, 127.80, 127.11,
125.74, 125.74, 124.62, 120.89, 21.08.
13C NMR (100 MHz, CDCl3): d = 147.52, 142.59, 138.14, 136.15,
135.25, 134.23, 130.56, 130.30, 129.72, 129.18, 128.91, 128.73,
128.20, 127.52, 126.31, 125.77, 125.70, 120.90.
HRMS: m/z calcd [M + H]+ for C20H15ClN3Se: 412.0120; found:
412.0116.
HRMS: m/z calcd [M + H]+ for C21H18N3Se: 392.0666; found:
392.0666.
1-[2-(Mesitylselanyl)phenyl]-4-phenyl-1H-1,2,3-triazole (3u)
Yield: 0.094 g (75%); brown solid; mp 162–163 °C.
1-{2-[(4-Methoxyphenyl)selanyl]phenyl}-4-phenyl-1H-1,2,3-
triazole (3p)
Yield: 0.115 g (94%); yellow solid; mp 138–140 °C.
1H NMR (400 MHz, CDCl3): d = 8.08 (s, 1 H), 7.92 (d, J = 7.6 Hz,
2 H), 7.47–7.41 (m, 5 H), 7.37–7.17 (m, 4 H), 6.85 (d, J = 7.6 Hz, 2
H), 3.78 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 160.38, 147.66, 137.77, 135.99,
131.61, 131.56, 130.42, 130.00, 128.81, 128.27, 126.89, 125.82,
125.76, 120.83, 118.09, 115.36, 55.22.
1H NMR (400 MHz, CDCl3): d = 8.13 (s, 1 H), 7.95 (d, J = 7.2 Hz,
2 H), 7.47 (t, J = 7.2 Hz, 2 H), 7.43 (dd, 1J = 8.0 Hz, 2J = 1.6 Hz, 1
H), 7.37 (t, J = 7.6 Hz, 1 H), 7.27 (dd, 1J = 7.2 Hz, 2J = 1.6 Hz, 1 H),
1
2
7.18 (td, J = 7.6 Hz, J = 1.2 Hz, 1 H), 6.98 (s, 2 H), 6.83 (dd,
1J = 8.0 Hz, 2J = 1.2 Hz, 1 H), 2.37 (s, 6 H), 2.29 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 147.70, 143.76, 139.72, 136.04,
131.03, 130.31, 130.17, 129.40, 129.08, 128.86, 128.31, 126.17,
125.98, 125.91, 125.89, 120.69, 24.01, 21.02.
HRMS: m/z calcd [M + H]+ for C23H22N3Se: 420.0979; found:
420.0973.
HRMS: m/z calcd [M + H]+ for C21H18N3OSe: 408.0615; found:
408.0609.
4-Phenyl-1-[4-(phenylselanyl)phenyl]-1H-1,2,3-triazole (3v)
Yield: 0.073 g (65%); white solid; mp 180–182 °C.
1-{2-[(4-Chlorophenyl)selanyl]phenyl}-4-phenyl-1H-1,2,3-tria-
zole (3q)
Yield: 0.108 g (88%); beige solid; mp 105–107 °C.
1H NMR (400 MHz, CDCl3): d = 8.06 (s, 1 H), 7.89 (d, J = 7.6 Hz,
2 H), 7.47–7.29 (m, 9 H), 7.24 (d, J = 7.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 147.74, 136.82, 136.28, 134.95,
133.10, 130.20, 130.09, 129.77, 129.70, 128.82, 128.32, 127.84,
127.13, 125.88, 125.80, 120.78.
1H NMR (400 MHz, CDCl3): d = 8.15 (s, 1 H), 7.89 (d, J = 8.4 Hz,
2 H), 7.67 (d, J = 8.4 Hz, 2 H), 7.57–7.54 (m, 4 H), 7.45 (t, J = 7.2
Hz, 2 H), 7.38–7.32 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 148.48, 135.88, 133.90, 133.28,
132.90, 130.09, 129.82, 129.62, 128.92, 128.48, 128.11, 125.84,
121.13, 117.34.
HRMS: m/z calcd [M + H]+ for C20H16N3Se: 378.0509; found:
378.0503.
HRMS: m/z calcd [M + H]+ for C20H15ClN3Se: 412.0120; found:
412.0114.
4-Phenyl-1-[2-(phenylthio)phenyl]-1H-1,2,3-triazole (3w)
Yield: 0.098 g (99%); white solid; mp 128–130 °C.
1H NMR (400 MHz, CDCl3): d = 8.09 (s, 1 H), 7.88–7.85 (m, 2 H),
7.53–7.51 (m, 1 H), 7.42 (t, J = 7.6 Hz, 2 H), 7.37–7.24 (m, 9 H).
13C NMR (100 MHz, CDCl3): d = 147.30, 136.34, 132.89, 132.84,
132.19, 132.02, 130.23, 130.11, 129.40, 128.72, 128.12, 128.09,
127.68, 126.84, 125.73, 121.58.
4-Phenyl-1-[2-(o-tolylselanyl)phenyl]-1H-1,2,3-triazole (3r)
Yield: 0.105 g (90%); white solid; mp 150–152 °C.
1H NMR (400 MHz, CDCl3): d = 8.03 (s, 1 H), 7.88 (d, J = 7.2 Hz,
2 H), 7.48–7.41 (m, 4 H), 7.36–7.32 (m, 2 H), 7.28–7.20 (m, 4 H),
7.08 (td, 1J = 7.6 Hz, 2J = 2.4 Hz, 1 H), 2.30 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 147.68, 141.59, 137.27, 136.17,
132.78, 130.60, 130.49, 130.15, 129.77, 129.67, 129.22, 128.83,
128.25, 127.49, 127.03, 126.28, 125.95, 120.89, 22.46.
HRMS: m/z calcd [M + H]+ for C20H16N3S: 330.1065; found:
330.1059.
HRMS: m/z calcd [M + H]+ for C21H18N3Se: 392.0666; found:
392.0665.
1,2-Bis[2-(4-phenyl-1H-1,2,3-triazol-1-yl)phenyl]diselenide (3x)
Yield: 0.108 g (60%); brown solid; mp 136–138 °C.
1-{2-[(2-Methoxyphenyl)selanyl]phenyl}-4-phenyl-1H-1,2,3-
triazole (3s)
Yield: 0.111 g (91%); yellow solid; mp 123–124 °C.
1H NMR (400 MHz, CDCl3): d = 8.33 (d, J = 8.4 Hz, 2 H), 7.93 (d,
J = 8.4 Hz, 2 H), 7.86–7.83 (m, 4 H), 7.63–7.59 (m, 2 H), 7.53–7.46
(m, 6 H), 7.39–7.35 (m, 2 H), 7.26 (s, 2 H).
1H NMR (400 MHz, CDCl3): d = 8.09 (s, 1 H), 7.84 (d, J = 7.2 Hz,
2 H), 7.51 (t, J = 7.6 Hz, 2 H), 7.41–7.37 (m, 3 H), 7.29 (t, J = 7.6
Hz, 2 H), 7.24–7.19 (m, 2 H), 6.82–6.78 (m, 2 H), 3.69 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 158.10, 147.29, 138.34, 135.16,
134.10, 130.52, 129.90, 129.59, 128.68, 128.26, 128.04, 127.57,
126.33, 125.81, 121.67, 121.20, 119.11, 111.17, 55.79.
13C NMR (100 MHz, CDCl3): d = 130.22, 130.17, 129.05, 128.87,
127.92, 127.55, 127.43, 127.40, 126.57, 125.88, 125.42, 115.97.
HRMS: m/z calcd [M – C14H10N3Se]+ for C14H10N3Se: 300.0040;
found: 300.0035.
1,2-Bis[2-(4-phenyl-1H-1,2,3-triazol-1-yl)phenyl]ditelluride
(3y)
Yield: 0.132 g (63%); brown solid; mp 131–133 °C.
HRMS: m/z calcd [M + H]+ for C21H18N3OSe: 408.0615; found:
408.0609.
Synthesis 2011, No. 15, 2397–2406 © Thieme Stuttgart · New York

2406
A. M. Deobald et al.
PAPER
1H NMR (400 MHz, DMSO-d6): d = 7.36–7.20 (m, 16 H), 7.12–
458. (d) Lee, T.; Cho, M.; Ko, S. Y.; Youn, H. J.; Baek, D.
J.; Cho, W. J.; Kang, C. Y.; Kirn, S. J. Med. Chem. 2007, 50,
585. (e) Parrish, B.; Emrick, T. Bioconjugate Chem. 2007,
18, 263.
7.08 (m, 4 H).
13C NMR (100 MHz, DMSO-d6): d = 141.42, 134.02, 129.08,
129.00, 128.45, 127.93, 127.14, 125.40, 125.04, 121.20, 117.32,
116.22.
HRMS: m/z calcd [M – C14H10N3Te]+ for C14H10N3Te: 349.9937;
found: 349.9931.
(6) (a) Nandivada, H.; Jiang, X.; Lahann, J. Adv. Mater. 2007,
19, 2197. (b) Lee, B. S.; Lee, J. K.; Kim, W. J.; Jung, Y. H.;
Sim, S. J.; Lee, J.; Choi, I. S. Biomacromolecules 2007, 8,
744.
(7) (a) Bastero, A.; Font, D.; Pericàs, M. A. J. Org. Chem. 2007,
72, 2460. (b) Chassaing, S.; Kumarraja, M.; Sido, A. S. S.;
Paie, P.; Sommer, J. Org. Lett. 2007, 9, 883.
5-(4-Methoxyphenyl)-4-phenyl-1-[2-(phenylselanyl)phenyl]-
1H-1,2,3-triazole (4)
To a soln of 5-iodo-4-phenyl-1-[2-(phenylselanyl)phenyl]-1H-
1,2,3-triazole (3m) (0.126 g, 0.25 mmol) in DMF (2.5 mL) was add-
ed Pd(OAc)2 (0.003 g, 5 mol%) and (4-methoxyphenyl)boronic
acid (0.053 g, 0.35 mmol) under Ar. The resulting soln was stirred
for 30 min at r.t., after which a soln of K3PO4 (1.2 mmol, 0.254 g)
in H2O (0.6 mL) was added. The mixture was then heated at reflux
temperature for 12 h, cooled to r.t., diluted with CH2Cl2 (20 mL) and
washed with brine (2 × 20 mL). The organic phase was separated,
dried over MgSO4, and concentrated under vacuum. The residue
was purified by flash chromatography (eluent: hexane–EtOAc,
80:20).
(8) Carlqvist, P.; Maseras, F. Chem. Commun. 2007, 748.
(9) Nepogodiev, S. A.; Dedola, S.; Marmuse, L.; Oliveira, M.
T.; Field, R. A. Carbohydr. Res. 2007, 342, 529.
(10) (a) Wirth, T. Organoselenium Chemistry, In Topics in
Current Chemistry; Springer-Verlag: Heidelberg, 2000,
208. (b) Paulmier, C. Selenium Reagents and Intermediates
in Organic Synthesis, In Organic Chemistry Series, Vol. 4;
Baldwin, J. E., Ed.; Pergamon Press: Oxford, 1986.
(c) Perin, G.; Lenardão, E. J.; Jacob, R. G.; Panatieri, R. B.
Chem. Rev. 2009, 109, 1277. (d) Freudendahl, D. M.;
Shahzad, S. A.; Wirth, T. Eur. J. Org. Chem. 2009, 1649.
(e) Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi,
C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.
(f) Braga, A. L.; Lüdtke, D. S.; Vargas, F. Curr. Org. Chem.
2006, 10, 1921.
Yield: 0.094 g (78%); yellowish solid; mp 117–119 °C.
1H NMR (400 MHz, CDCl3): d = 8.44 (d, J = 8.4 Hz, 1 H), 7.71 (dd,
1J = 7.6 Hz, 2J = 1.2 Hz, 1 H), 7.44–7.39 (m, 1 H), 7.28–7.05 (m, 15
H), 5.03 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 170.25, 139.17, 139.06, 138.65,
137.93, 130.97, 130.68, 129.83, 129.46, 128.87, 128.74, 126.85,
126.75, 124.98, 120.38, 118.62, 74.94.
(11) (a) Parnham, M. J.; Graf, E. Prog. Drug Res. 1991, 36, 9.
(b) Mugesh, G.; du Mont, W. W.; Sies, H. Chem. Rev. 2001,
101, 2125. (c) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T.
Chem. Rev. 2004, 104, 6255. (d) Alberto, E. E.;
Nascimento, V.; Braga, A. L. J. Braz. Chem. Soc. 2010, 21,
2032.
HRMS: m/z calcd [M + H]+ for C27H22N3OSe: 484.0928; found:
484.0922.
(12) (a) Braga, A. L.; Ludtke, D. S.; Vargas, F.; Braga, R. C.
Synlett 2006, 1453. (b) Braga, A. L.; Vargas, F.; Sehnem, J.
A.; Braga, R. C. J. Org. Chem. 2005, 70, 9021. (c) Braga,
A. L.; Paixao, M. W.; Ludtke, D. S.; Silveira, C. C.;
Rodrigues, O. E. D. Org. Lett. 2003, 5, 2635. (d) Braga, A.
L.; Paixao, M. W.; Marin, G. Synlett 2005, 1975. (e) Braga,
A. L.; Ludtke, D. S.; Sehnem, J. A.; Alberto, E. E.
Tetrahedron 2005, 61, 11664. (f) Braga, A. L.; Rodrigues,
O. E. D.; Paixão, M. W.; Appelt, H. R.; Silveira, C. C.;
Bottega, D. P. Synthesis 2002, 2338.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.
Acknowledgment
We are grateful to CAPES, CNPq (INCT Catálise and INCT
NANOBIOSIMES), FAPESC and FAPERGS (ARD 10/0130-3)
for financial support.
(13) For a previous communication, see: Deobald, A. M.;
Camargo, L. R. S.; Tabarelli, G.; Hörner, M.; Rodrigues, O.
E. D.; Alves, D.; Braga, A. L. Tetrahedron Lett. 2010, 51,
3364.
References
(1) Grimett, M. R. In Comprehensive Organic Chemistry;
Barton, D.; Ollis, W. D., Eds.; Pergamon Press: Oxford,
1979.
(14) (a) Bräse, S.; Gil, C.; Knepper, K.; Zimmermann, V. Angew.
Chem. Int. Ed. 2005, 44, 5188. (b) Scriven, E. F. V.;
Turnbull, K. Chem. Rev. 1988, 88, 297. (c) L’Abbé, G.
Chem. Rev. 1969, 69, 345.
(2) Huisgen, R. Angew. Chem. 1963, 75, 604.
(3) (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless,
K. B. Angew. Chem. Int. Ed. 2002, 41, 2596. (b) Krasinski,
A.; Radic, Z.; Manetsch, R.; Raushel, J.; Taylor, P.;
Sharpless, K. B.; Kolb, H. C. J. Am. Chem. Soc. 2005, 127,
6686. (c) Lee, L. V.; Mitchell, M. L.; Huang, S.; Fokin, V.
V.; Sharpless, K. B.; Wong, C. J. Am. Chem. Soc. 2003, 125,
9588. (d) Hein, J. E.; Tripp, J. P.; Krasnova, L. B.; Sharpless,
K. B.; Fokin, V. V. Angew. Chem. Int. Ed. 2009, 48, 1.
(e) Tornøe, C. W.; Christensen, C.; Meldal, M. J. Org.
Chem. 2002, 67, 3057. (f) Shao, C.; Cheng, G.; Su, D.; Xu,
J.; Wang, X.; Hu, Y. Adv. Synth. Catal. 2010, 352, 1587.
(4) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int.
Ed. 2001, 40, 2004.
(15) (a) Riela, S.; Aprile, C.; Gruttadauria, M.; Lo Melo, P.;
Noto, R. Molecules 2005, 10, 383. (b) Ward, V. R.; Cooper,
N. A.; Ward, A. P. J. Chem. Soc., Perkin Trans. 1 2001, 944.
(c) Broggini, G.; Molteni, G.; Zucchi, G. Synthesis 1995,
647.
(16) (a) Back, T. G.; Bethell, R. J.; Parvez, M.; Taylor, J. A.;
Wehrli, D. J. Org. Chem. 1999, 64, 7426. (b) Tiecco, M.;
Testaferri, L.; Santi, C.; Tomassini, C.; Marini, F.; Bagnoli,
L.; Temperini, A. Angew Chem. Int. Ed. 2003, 42, 3131.
(17) Roth, P. J.; Kessler, D.; Zentel, R.; Theato, P. J. Polym. Sci.,
Part A: Polym. Chem. 2009, 47, 3118.
(18) (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(b) Barancelli, D. A.; Alves, D.; Prediger, P.; Stangherlin, E.
C.; Nogueira, C. W.; Zeni, G. Synlett 2008, 119.
(19) Brandsma, L. Preparative Acetylene Chemistry, 3rd ed.;
Elsevier: Amsterdam, 1988.
(5) (a) Tron, G. C.; Pirali, T.; Billington, R. A.; Canonico, P. L.;
Sorba, G.; Genazzani, A. A. Med. Res. Rev. 2008, 28, 278.
(b) Hein, C. D.; Liu, X.-M.; Wang, D. Pharm. Res. 2008, 25,
2216. (c) Xie, J.; Seto, C. T. Bioorg. Med. Chem. 2007, 15,
Synthesis 2011, No. 15, 2397–2406 © Thieme Stuttgart · New York