Synthesis of Fully Functionalized 5-Selanyl-1,2,3-triazoles: Copper-Catalysed Three-Component Reaction of Ethynylstibanes, Organic Azides, and Diaryl Diselenides

Article abstract of DOI:10.1002/ejoc.201701389

A simple, general method for the synthesis of fully substituted 5-selanyl-1,2,3-triazoles is described. In the presence of CuI (10 mol-%) and 1,10-phenanthroline (10 mol-%), a three-component reaction of ethynylstibanes, organic azides, and diaryl diselenides gave 5-selanyltriazoles in moderate-to-excellent yields. Under aerobic conditions, the reaction proceeded efficiently, and both of the two selanyl groups were transferred from the diaryl diselenide to the product. In this three-component reaction, ethynylstibanes, containing an antimony atom, gave better results than various alkynes containing other typical elements, such as silicon, tin, and tellurium.

Full text of DOI:10.1002/ejoc.201701389

A Journal of
Accepted Article
Title: Synthesis of Fully Functionalized 5-Selanyl-1,2,3-
triazoles: Copper-Catalyzed Three-Component Reaction of
Ethynylstibanes, Organic Azides, and Diaryl Diselenides
Authors: Mizuki Yamada, Mio Matsumura, Fumina Takino, Yuki
Murata, Yuka Kurata, Masatoshi Kawahata, Kentaro
Yamaguchi, Naoki Kakusawa, and Shuji Yasuike
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701389
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701389
Supported by

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Synthesis of Fully Functionalized 5-Selanyl-1,2,3-triazoles: Copper-Catalyzed Three-Component
Reaction of Ethynylstibanes, Organic Azides, and Diaryl Diselenides
Mizuki Yamada,[a] Mio Matsumura,[a] Fumina Takino,[a] Yuki Murata,[a] Yuka Kurata,[a] Masatoshi
Kawahata,[b] Kentaro Yamaguchi,[b] Naoki Kakusawa,[c] Shuji Yasuike*[a]
[a] School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku,
Nagoya 464-8650, Japan
[b] Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido,
Sanuki, Kagawa 769-2193, Japan
[c] Faculty of Pharmaceutical Sciences, Hokuriku University, Ho-3 Kanagawa-machi, Kanazsawa
920-1181, Japan
*Corresponding authors.
Address: School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho,
Chikusa-ku, Nagoya 464-8650, Japan
Tel: +81-52-757-6774
E-mail address: s-yasuik@dpc.agu.ac.jp (S. Yasuike)
URL: http://www.phar.agu.ac.jp/lab/med_chem/
1
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Abstract
A simple general method for the synthesis of fully substituted 5-selanyl-1,2,3-triazoles is described.
In the presence of CuI (10 mol%) and 1,10-phenanthroline (10 mol%), three-component reaction of
ethynylstibanes, organic azides and diaryl diselenides afforded 5-selanyltriazoles in moderate-to-
excellent yields. Under an aerobic conditions, the reaction proceeded efficiently in that two selanyl
groups were transferred from the diaryl diselenide to the products. In this three-component reaction,
ethynylstibanes having antimony atom gave superior results compared to various alkynes having
other typical elements such as silicon, tin, and tellurium.
Key words: three-component reaction, 5-selanyl-1,2,3-triazole, ethynylstibane, organic azide, diaryl
diselenide, copper catalyst
2
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Introduction
Organoselenium compounds have garnered attention in various areas of science, such as biology and
organic synthesis.[1,2] Among them, diaryl selenides have been of particular interest in the last two
decades owing to their wide applicability in biological and pharmaceutical fields because of their
anticancer, antitumor, antiviral, antimicrobial, and antioxidant activities.[3] Recently, interest in
selenides having a heterocyclic ring is rising due to their biological activities. For instance, 4-
arylselanyl-7-chloroquinolines act as potential antioxidants,[4] selenofonsartan analogues having
imidazolyl group inhibit Angiotensin II type 1 (AT1) receptor,[5] and 3-(arylselanyl)selenophenes
exhibit antidepressant-like properties.[6] Several methods have been developed for the synthesis of
unsymmetrical diaryl selenides. Transition-metal-catalyzed C–Se bond formation is one of the most
popular methods for the synthesis of organoselenides.[1c,7] Among them, diaryl diselenide is superior
to other selenium reagents (selenol, arylselenium bromide, and alkyltin selenide) as the selanyl source
for the synthesis of diaryl selenides in terms of odor, stability, and toxicity. For instance, it is known
that Cu-catalyzed C(aryl)–Se bond formation by reacting diaryl diselenides with aryl halides,[8] aryl
boronic acids,[9] and triarylbismuthanes[10] led to the formation of unsymmetrical diaryl selenides.
Synthesis of fully functionalized 1,2,3-triazoles have drawn considerable interest because of their
potential in medicinal chemistry and as pharmacophores of numerous bioactive compounds.[11]
Among these, the synthesis of fully functionalized 1,2,3-triazoles having selenium atom as a
substituent at the C-5 position was recently attempted using transition-metal-mediated azide-alkyne
cycloaddition with high levels of regioselectivity. In 2009, Benhida et al. carried out the three-
component reaction of terminal alkynes, ribosyl azides, and phenylselanyl bromide in the presence
of CuI (1.2 eq) and N,N-diisopropylethylamine (3 eq).[12] In 2014, Sun et al. reported the cycloaddition
of butylethynyl phenyl selenide with benzyl azide using iridium catalyst [Ir(cod)Cl]2 (2 mol%).[13] In
2016, Xu et al. carried out the three-component reaction of a terminal alkyne, benzyl azide, and
phenylselanyl benzenesulfonate (PhSO2SePh) in the presence of CuI (20 mol%) and LiOtBu (2 eq).[14]
However, these reactions have low applicability of the 5-position selanyl group because the selenium
reagents being used are not always commercially available and require complicated preparation steps.
3
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
In 2016, Ackermann et al. reported an efficient and versatile method using Cu-catalyzed C–H
selanylation of 1,4-disubstituted 1,2,3-triazoles with diaryl diselenides.[15] One drawback of this
reaction is the requirement of an amide moiety at the C-4 position in triazoles for C–H activation. To
the best of our knowledge, synthesis of fully functionalized 5-selanyl-1,2,3-triazoles using Cu-
catalyzed C(aryl)–Se bond formation based on a selenium-induced reaction via exchange of typical
elements has not been reported. Recently, we found that Cu-catalyzed azide-alkyne cycloaddition of
ethynylstibanes with organic azides can be converted to fully substituted 5-organostibano-1,2,3-
triazoles bearing antimony, [16] which could be employed as versatile building blocks in chemical
synthesis.[17] As a follow up to our studies, we present here the synthesis of fully functionalized 5-
selanyl-1,2,3-triazoles under aerobic conditions by Cu-catalyzed three-component reaction of
ethynylstibanes, organic azides, and diaryl diselenides.
Results and Discussion
We initially focused our attention on the determination of optimal conditions for the synthesis of 5-
selanyl-1,2,3-triazole 4a using benzyl azide 2a, di-p-tolyl diselenide 3a and various alkynes 1 having
typical elements such as Si, Sn, Sb, and Te. The results of the experiments to identify suitably active
alkynes, catalysts, ligands, and solvents for the three-component reaction, are summarized in Table
1. The yield and reaction time for reaction of various alkynes 1a-d (0.5 mmol), 2a (0.5 mmol), and
o
3a (0.25 mmol) under aerobic conditions in DMSO at 60 C using CuI (0.05 mmol) as catalyst and
1,10-phenanthroline (0.05 mmol) as ligand are given as entries 1-4 (Table 1). Ethynylstibane 1c was
found to be the best alkyne for the reaction in terms of the yield of the expected triazole 4a, the
reaction time, and the yield of byproduct 5a. It should be emphasized that in the present three-
component reaction, both the selanyl groups were transferred from diselenide to the coupling product
4a. When copper acetylide 1e was used instead of ethynylstibane 1c, the reaction time prolonged and
the yield decreased (entry 5). Additionally, ethynylbenzene 1f was found inactive for this reaction
(entry 6). Several available Cu catalysts were then screened for their suitability in the reaction of 1c
with 2a and 3a (entries 3, 7-15). CuI was the best catalyst for this reaction in terms of the yield (87%)
4
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
of 4a and reaction time (3 h). Various ligands were screened next (entries 3, 16-24), among which
1,10-phenanthroline was the most effective. Screening of solvents showed that the reaction proceeded
efficiently in DMSO (87%), DMF (69%), NMP (68%), and 1,2-DCE (63%), whereas CH3CN, EtOH,
THF, and toluene were inefficient reaction solvents (entries 3, 25-32). The reaction at room
temperature required a long reaction time of 24 h (entry 33). When the reactions were performed
under argon and oxygen, the product was obtained in a lower yields (entries 34 and 35). Results
suggested that presence of oxygen and water in the air are necessary for the reaction. The reaction is
easy to operate under aerobic conditions, which are thus considered excellent reaction conditions.
Catalyst loading influenced the yield of products and the reaction time. Decreasing the loading of CuI
from 10 mol% to 5 mol% and 1 mol% significantly reduced the yield of 4a and reaction time
prolonged (entries 36 and 37). The best result was obtained under aerobic conditions at 60 oC when
1c, 2a, and 3a were treated with CuI and 1,10-phenanthroline in DMSO. The regiochemistry of 5-
1
selanyltriazole 4a was elucidated by H NMR spectroscopy and confirmed by single-crystal X-ray
analysis (Figure 1). A nuclear Overhauser effect (NOE) was observed between the benzylic protons
and the aromatic protons of the p-tolyl group.
Table 1. Optimization of reaction conditions.[a]
Yield (%)[b]
En.
M
Cu cat.
Ligand
1,10-Phen.
Solvent
DMSO
Time (h)
4a
62
3
5a
19
26
8
1
1a: SiMe3
CuI
4
3
2
1b: Sn(nBu)3
1c: SbPh2
1d: TenBu
1e: Cu
CuI
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
3
CuI
3
87
32
61
30
65
73
47
58
44
23
4
CuI
24
24
24
3
---
---
---
25
26
26
35
31
38
5
CuI
6
1f: H
CuI
7
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
CuBr
CuCl
8
2
9
CuOAc
Cu2O
2
10
11
12
4
CuBr2
2
Cu(OAc)2
3
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33[c]
34[d]
35[e]
36
37
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
1c: SbPh2
CuO
CuSO4
---
1,10-Phen.
1,10-Phen.
1,10-Phen.
PPh3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
24
4
30
47
25
<5
50
28
49
69
75
28
17
33
46
66
57
28
31
14
15
28
28
34
13
9
23
7
CuI
39
CuI
TEA
2
26
23
56
81
5
CuI
Proline
24
23
2
CuI
EDA
CuI
2,2’-Bipyridyl
DMEDA
CuI
23
4
CuI
TMEDA
48
23
42
69
68
46
25
59
25
63
25
71
37
36
62
53
CuI
PMDTA
3
CuI
---
3
CuI
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen.
1,10-Phen. (5%)
1,10-Phen. (1%)
2
CuI
NMP
4
CuI
CH3CN
1,4-Dioxane
EtOH
4
CuI
24
23
23
3
CuI
CuI
THF
CuI
DCE
CuI
Toluene
DMSO
DMSO
DMSO
DMSO
DMSO
24
24
24
2
CuI
CuI
26
35
33
31
CuI
CuI (5%)
CuI (1%)
7
24
[a] Reaction conditions: 1 (0.5 mmol), 2a (0.5 mmol), 3a (0.25 mmol). [b] Isolated yield. [c] At room temperature. [d] Under argon. [e] Under O2.
Figure 1. Ortep drawing of 4a with 50% probability. All hydrogen atoms are omitted for clarity.
To demonstrate the efficiency and generality of this three-component reaction, the reactions of various
ethynylstibanes (1: 0.5 mmol), organic azides (2: 0.5 mmol), and diaryl diselenides (3: 0.25 mmol)
were investigated under aerobic conditions in DMSO using the catalytic system of CuI (10 mol%)
6
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
and 1,10-phenanthroline (10 mol%) at 60 °C. Ethynylstibanes 1 of the key starting material could be
easily prepared according to the general method used previously.[18] The terminal alkynes were treated
with n-BuLi in dry ether under an argon atmosphere at 0 °C, and followed by trapping with
diphenylantimony bromide to afford arylethynyl, vinylethynyl, and alkylethynyl compounds in 44–
83% yields. The results of three-component reaction are summarized in Table 2. Reactions of
ethynylstibane 1c, benzyl azide 2a, and diaryl diselenides 3 gave the corresponding 5-selanyl-1,2,3-
triazoles 4a-m in good-to-excellent yields (60–98%), except for the benzyl selenide derivative 4n
(38%). For 4a-f, the substituent on the benzene ring of diselenides did not affect the progress of the
reaction. The reaction of sterically hindered ortho-substituted diselenides gave the corresponding
selenides 4g-k including CH2NMe2 and acetamide moieties without any difficulty. With diaryl
diselenides having heterocyclic ring, this reaction gave 4l and 4m. Dibenzyl diselenide having benzyl
moiety as the alkyl group resulted in lower yield of 4n than diaryl diselenides. Various ethynylstibanes
1 were then reacted with benzyl azide 2a and diphenyl diselenide under the same reaction conditions.
Ethynylstibanes 1 with functional groups such as aryl, vinyl, and alkyl also afforded the
corresponding products 4o-s in satisfactory yields. The electronic nature of the substituents in 1 did
not affect the outcome of the reaction. Furthermore, various organic azides 2 bearing cinnamyl,
(ethoxycarbonyl)methyl, 1-naphthalenemethyl and (phenylthio)methyl groups were reacted with 1c
and diphenyl diselenide to afford the corresponding triazoles 4t-w in moderate yields. However, the
reaction with aryl-azides such as 4-methylphenyl- and 4-cyanophenyl-azide gave a complex mixture.
We have recently reported that 5-stibanotriazoles could not be obtained in the Cu-catalyzed [3+2]
cycloaddition of (phenylethynyl)di-p-tolylstibane with aryl-azides.[16] Even in the three-component
reaction, there might be a problem with the cyclization step.
7
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Table 2. Study of substrate scope[a,b]
4b: 77% (3 h)
4e: 82% (3 h)
4i: 73% (2 h)
4m: 60% (2 h)
4q: 73% (1 h)
4u: 52% (4 h)
4a: 87% (3 h)
4f: 98% (3 h)
4j: 70% (1 h)
4n: 38% (2 h)
4r: 74% (2 h)
4v: 62% (3 h)
4c: 65% (2 h)
4g: 84% (4 h)
4k: 65% (2 h)
4o: 75% (4 h)
4s: 83% (2 h)
4w: 59% (2 h)
4d: 71% (3 h)
4h: 81% (3 h)
4l: 67% (1 h)
4p: 73% (3 h)
4t: 57% (2 h)
[a] 1 (0.5 mmol), 2 (0.5 mmol), 3 (0.25 mmol), CuI (0.05 mmol), 1,10-Phen. (0.05 mmol).
[b] Isolated yield.
8
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Acontrol experiment was conducted to propose a reaction mechanism. The reaction of ethynylstibane
1c with di-p-tolyl diselenide 3a under standard conditions afforded the ethynylselenide 6 in 87% yield
(Eq. 1). However, the cycloaddition of 6 with benzyl azide 2a did not progress (Eq. 2). The type of
reaction might differ between three- and stepwise two-component reactions. For instance, Xu et al.
reported Cu-catalyzed three-component reaction of terminal alkynes, benzyl azide, and
benzenesulfonothioate for the synthesis of fully functionalized 5-sulfanyltriazoles.[14] The two-
component reaction of phenylacetylene with benzenesulfonothioate afforded the ethynylsulfide in
high yield. However, the reaction of ethynylsulfide and benzyl azide does not proceed. The reaction
of 5-stibanotriazole 7a[17a] with 3a obtained the corresponding 5-selanyltriazole 4a in high yield (Eq.
3). On the other hand, 4a could not be produced by the reaction of 5a with 3a (Eq. 4). Heating of
ethynylstibane 1c without azide and diselenide under standard condition recovered 1c at isolated yield
86% (Eq. 5). In this reaction, trace amounts of ethynylbenzene were observed in gas-liquid
chromatography, while 1,4-diphenylbuta-1,3-diyne was not detected. Three-component reaction of
1c, 2a, and 3a with 1 equivalent of TEMPO as radical scavenger gave 5-selanyltriazole 4a in
satisfactory yield (81%).
9
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Scheme 1. Control experiments
Based on the above control experiments, a possible mechanism for this three-component reaction is
shown in Scheme 2. This reaction involves the formation of 5-stibanotriazole 7 from ethynylstibane
1 and azide 2 in the presence of a Cu catalyst. [16,17b] Moreover, diaryl diselenide 3 reacts with
bimetallic complex [(phen)2CuI2] A to generate Cu(III) intermediate B.[19] Compound 7 would attack
the intermediate B at the 5-position on the triazole to form intermediate C, which undergoes reductive
elimination to give the intermediate D with regeneration of the Cu complex. The aryl selenide anion
attacks the antimony to generate 5-selanyltriazole 4 and Ph2Sb–SeAr, which is hydrolyzed with H2O
in the air and converted to selenol E and Ph2SbOH. Selenol E is converted to diselenide 3 by air
oxidation. Therefore, the reaction proceeds with 0.5 equivalents of diselenide and two selanyl groups
can be used for the reaction.
10
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Scheme 2. Proposed mechanism
In conclusion, we developed simple Cu-catalyzed three-component reaction for the synthesis of fully
substituted 5-selanyl-1,2,3-triazoles under aerobic conditions without the need for any additives. The
reaction is atom-economic and both selanyl groups on the diaryl diselenide participated in the reaction.
Ethynylstibanes, organic azides, and diselenides with different functional groups afforded the
corresponding products with satisfactory yields. Detailed mechanistic studies of this three-component
reaction and its application to medicinal chemistry are in progress and will be reported in the future.
Experimental Section
General Information
Melting points were measured on a Yanagimoto micro melting point hot-stage apparatus (MP-S3)
1
and reported as uncorrected values. H NMR (TMS: δ: 0.00 or CH2Cl2: 5.30 ppm as an internal
standard) and 13C NMR (CDCl3: δ: 77.00 or DMSO-d6: δ: 39.52 ppm as an internal standard) spectra
were recorded on JEOLJNM-AL400 (400 MHz and 100 MHz) spectrometers in CDCl3. Mass spectra
were obtained on a JEOL JMP-DX300 instrument (70 eV, 300 mA). IR spectra were recorded on a
11
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Shimadzu FTIR-8400S spectrophotometer and reported in terms of frequency of absorption (cm-1).
Only selected IR bands are reported. Chromatographic separations were carried out using Silica Gel
60N (Kanto Chemical Co., Inc.) under the solvent system stated. Thin-layer chromatography (TLC)
was performed using Merck Pre-coated TLC plates (silica gel 60 F254). Compound 1b, 1e, 1f, 2a,
2e, 3c, 3n and each reagents were purchased from Sigma-Aldrich Japan, Wako Pure Chemical
Industries and Tokyo Chemical Industry Co., Ltd. Known compounds were prepared according to the
published procedures (1a[20], 1c, 1g, 1h, 1k[18], 1d[21], 2b, 2c[22], 2d[23], 3a, 3b, 3d, 3g, 3h[24], 3e[25]
,
3f[26], 3i[27], 3j[28], 3l[29], 3m[30]). Preparations of 1i, 1j, 3k were described in Supporting information.
General procedure for the synthesis of 5-selanyltriazole (4a-w)
CuI (9.5 mg, 0.05 mmol, 10 mol%), 1,10-phenanthroline (9.0 mg, 0.05 mmol, 10 mol%),
ethynylstibane (1) (0.5 mmol), organic azide (2) (0.5 mmol, 1 eq.) and diselenide (3) (0.25 mmol, 0.5
eq.) dissolved in DMSO (5 mL) and it was stirred at 60 °C. The reaction time was determined by
monitoring with TLC. The reaction mixture was diluted with CH2Cl2 (10 mL) and water (10 mL).
The phases were separated and aqueous layer was extracted with CH2Cl2 (30 mL x 2). The combined
organic layer was washed with brine, dried over MgSO4 and concentrated under reduced pressure.
The residue was purified by silica gel chromatography (n-hexane/AcOEt).
1-Benzyl-4-phenyl-5-(p-tolylselanyl)-1H-1,2,3-triazole (4a)
176 mg (87%), Colorless plate. Mp 109.5-110 °C (CH2Cl2 / hexane); Rf = 0.3 (hexane-AcOEt, 5 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.8 Hz, 2H, Ar-H), 7.41-7.32 (m, 3H, Ar-H), 7.24-7.22
(m, 5H, Ar-H), 6.93-6.88 (m, 4H, Ar-H), 5.64 (s, 2H, CH2), 2.23 (s, 3H, CH3). 13C NMR (100 MHz,
CDCl3): δ = 151.3 (s), 137.4 (s), 134.9 (s), 130.6 (s), 130.4 (d), 129.7 (d), 128.6 (d), 128.44 (d), 128.40
(d), 128.0 (d), 127.8 (d), 127.5 (d), 125.7 (s), 118.3 (s), 53.0 (t), 20.9 (q). FTIR (KBr): 1559, 1541,
1508, 1474, 1456 cm-1. HRMS: m/z [M]+ calcd for C22H19N3Se: 405.0744. Found: 405.0742.
1-Benzyl-5-[(4-methoxyphenyl)selanyl]-4-phenyl-1H-1,2,3-triazole (4b)
12
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
162 mg (77%), Colorless needle. Mp 67-68 °C (Et2O); Rf = 0.3 (hexane-AcOEt, 4 : 1). 1H NMR (400
MHz, CDCl3): δ = 7.56 (dd, J = 7.6, 2.0 Hz, 2H, Ar-H), 7.44-7.36 (m, 3H, Ar-H), 7.26-7.19 (m, 5H,
Ar-H), 6.96 (d, J = 8.6 Hz, 2H, Ar-H), 6.63 (d, J = 8.9 Hz, 2H, Ar-H), 5.66 (s, 2H, CH2), 3.71 (s, 3H,
CH3). 13C NMR (100 MHz, CDCl3): δ = 159.4 (s), 151.0 (s), 135.0 (s), 132.2 (d), 130.7 (s), 128.7 (d),
128.43 (d), 128.40 (d), 128.1 (d), 127.7 (d), 127.6 (d), 119.14 (s), 119.09 (s), 115.3 (d), 55.3 (q), 53.0
(t). FTIR (KBr): 1653, 1559, 1489, 1456, 1248 cm-1. HRMS: m/z [M]+ calcd for C22H19N3OSe:
421.0693. Found: 421.0701.
1-Benzyl-4-phenyl-5-(phenylselanyl)-1H-1,2,3-triazole[14] (4c)
146 mg (75%), Colorless needle. Mp 91.5-92 °C (CH2Cl2 / hexane); Rf = 0.3 (hexane-AcOEt, 5 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.3 Hz, 2H, Ar-H), 7.42-7.33 (m, 3H, Ar-H), 7.25-7.20
(m, 5H, Ar-H), 7.17-7.09 (m, 3H, Ar-H), 6.97 (dd, J = 7.9, 0.7 Hz, 2H, Ar-H), 5.66 (s, 2H, CH2). 13C
NMR (100 MHz, CDCl3): δ = 151.6 (s), 134.5 (s), 130.5 (s), 129.7 (d), 129.6 (s), 128.6 (d), 129.2 (d),
128.5 (d), 128.4 (d), 128.2 (d), 127.9 (d), 127.4 (d), 127.2 (d), 117.8 (s), 53.1 (t). HRMS: m/z [M]+
calcd for C21H17N3Se: 391.0588. Found: 391.0590.
1-Benzyl-5-[(4-chlorophenyl)selanyl]-4-phenyl-1H-1,2,3-triazole (4d)
151 mg (71%), Colorless plate. Mp 142-144 °C (CH2Cl2 / hexane); Rf = 0.5 (hexane-AcOEt, 5 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.01 (dd, J = 7.9, 1.0 Hz, 2H, Ar-H), 7.25-7.15 (m, 5H, Ar-H), 7.45-
7.33 (m, 3H, Ar-H), 7.02 (d, J = 6.6 Hz, 2H, Ar-H), 6.82 (d, J = 6.6 Hz, 2H, Ar-H), 5.67 (s, 2H, CH2).
13C NMR (100 MHz, CDCl3): δ = 151.7 (s), 134.6 (s), 133.5 (s), 130.5 (d), 130.3 (s), 129.7 (d), 128.7
(d), 128.5 (d), 128.2 (d), 127.8 (d), 127.6 (s), 127.4 (d), 117.4 (s), 53.3 (t). FTIR (KBr): 3084, 1559,
1474, 1456, 1227 cm-1. HRMS: m/z [M]+ calcd for C21H16ClN3Se: 425.0198. Found: 425.0201.
Ethyl 4-[(1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)selanyl]benzoate (4e)
190 mg (82%), Colorless prism. Mp 112.5-113 °C (CH2Cl2 / hexane); Rf = 0.3 (hexane-AcOEt, 4 : 1).
1H NMR (400 MHz, CDCl3): δ = 7.99 (dd, J = 7.8, 1.5 Hz, 2H, Ar-H), 7.73 (d, J = 8.3 Hz, 2H, Ar-
13
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
H), 7.41-7.32 (m, 3H, Ar-H), 7.23-7.18 (m, 5H, Ar-H), 6.93 (d, J = 8.3 Hz, 2H, Ar-H), 5.67 (s, 2H,
CH2), 4.33 (q, J = 7.0 Hz, 2H, CH2), 1.36 (t, J = 7.1 Hz, 3H, CH3). 13C NMR (100 MHz, CDCl3): δ
= 165.8 (s), 152.0 (s), 136.1 (s), 134.5 (s), 130.5 (d), 130.2 (s), 129.1 (s), 128.74 (d), 128.68 (d), 128.5
(d), 128.3 (d), 128.0 (d), 127.9 (d), 127.3 (d), 116.5 (s), 61.1 (t), 53.3 (t), 14.3 (q). FTIR (KBr): 3028,
1715, 1589, 1396, 1271 cm-1. HRMS: m/z [M]+ calcd for C24H21N3O2Se: 463.0799. Found: 463.0803.
1-Benzyl-4-phenyl-5-{[4-(trifluoromethyl)phenyl]selanyl}-1H-1,2,3-triazole (4f)
224 mg (98%), Colorless needle. Mp 103-104 °C (CH2Cl2 / hexane); Rf = 0.5 (hexane-AcOEt, 5 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.01 (dd, J = 6.6, 1.6 Hz, 2H, Ar-H), 7.42-7.34 (m, 3H, Ar-H), 7.26
(d, J = 8.6 Hz, 2H, Ar-H), 7.18-7.10 (m, 5H, Ar-H), 6.93 (d, J = 8.2 Hz, 2H, Ar-H), 5.68 (s, 2H, CH2).
13C NMR (100 MHz, CDCl3): δ = 152.2 (s), 134.7 (s), 134.3 (s), 130.1 (s), 129.0 (s, 2JC,F = 33 Hz),
128.8 (d), 128.62 (d), 128.58 (d), 128.4 (d), 128.3 (d), 127.9 (d), 127.3 (d), 126.2 (d, 3JC,F = 4.1 Hz),
123.7 (s, 1JC,F = 271 Hz), 116.3 (s), 53.4 (t). FTIR (KBr): 2922, 1474, 1456, 1398, 1325 cm-1. HRMS:
m/z [M]+ calcd for C22H16F3N3Se: 459.0462. Found: 459.0459.
1-Benzyl-5-(1-naphthylselanyl)-4-phenyl-1H-1,2,3-triazole (4g)
185 mg (84%), Colorless prism. Mp 88-90 °C (CH2Cl2 / hexane); Rf = 0.3 (hexane-AcOEt, 4 : 1). 1H
NMR (400 MHz, CDCl3): δ = 8.04 (dd, J = 7.8, 1.5 Hz, 2H, Ar-H), 8.01-7.99 (m, 1H, Ar-H), 7.84-
7.82 (m, 1H, Ar-H), 7.65 (d, J = 7.8 Hz, 1H, Ar-H), 7.55-7.52 (m, 2H, Ar-H), 7.39-7.31 (m, 3H, Ar-
H), 7.17-7.11 (m, 5H, Ar-H), 7.06 (t, J = 7.8 Hz, 1H, Ar-H), 6.80 (d, J = 6.8 Hz, 1H, Ar-H), 5.61 (s,
2H, CH2). 13C NMR (100 MHz, CDCl3): δ = 152.0 (s), 134.6 (s), 134.1 (s), 132.0 (s), 130.4 (s), 128.8
(d), 128.6 (d), 128.5 (d) x 2, 128.3 (s), 128.1 (d), 127.9 (d), 127.8 (d), 127.6 (d), 127.5 (d), 126.9 (d),
126.5 (d), 126.2 (d), 125.1 (d), 117.3 (s), 53.2 (t). FTIR (KBr): 3026, 1559, 1506, 1472, 1456 cm-1.
HRMS: m/z [M]+ calcd for C25H19N3Se: 441.0744. Found: 441.0747.
1-Benzyl-4-phenyl-5-(o-tolylselanyl)-1H-1,2,3-triazole (4h)
164 mg (81%), Colorless plate. Mp 82-83 °C (Et2O); Rf = 0.4 (hexane-AcOEt, 4 : 1). 1H NMR (400
14
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
MHz, CDCl3): δ = 8.00 (dd, J = 8.3, 2.0 Hz, 2H, Ar-H), 7.41-7.33 (m, 3H, Ar-H), 7.22 (s, 5H, Ar-H),
7.13 (d, 1H, J = 7.3 Hz, Ar-H), 7.06 (t, 1H, J = 7.6 Hz, Ar-H), 6.82 (t, 1H, J = 7.6 Hz, Ar-H), 6.47 (d,
J = 7.8 Hz, 1H, Ar-H), 5.62 (s, 2H, CH2), 2.37 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3): δ = 152.0
(s), 136.4 (s), 134.7 (s), 130.6 (d), 130.5 (s), 128.6 (d), 128.5 (d), 128.4 (d), 128.17 (d), 128.16 (d),
127.9 (d), 127.4 (d), 127.3 (d), 126.9 (d), 117.2 (s), 53.1 (t), 21.9 (q). FTIR (KBr): 3053, 1497, 1464,
1451, 1425 cm-1. HRMS: m/z [M]+ calcd for C22H19N3Se: 405.0744. Found: 405.0740.
1-Benzyl-5-(mesitylselanyl)-4-phenyl-1H-1,2,3-triazole (4i)
159 mg (73%), Colorless prism. Mp 107-108.5 °C (CH2Cl2 / hexane); Rf = 0.4 (hexane-AcOEt, 4 : 1).
1H NMR (400 MHz, CDCl3): δ = 7.85 (dd, J = 6.6, 1.5 Hz, 2H, Ar-H), 7.41-7.32 (m, 3H, Ar-H), 7.26-
7.23 (m, 3H, Ar-H), 7.01-6.99 (m, 2H, Ar-H), 6.73 (s, 2H, Ar-H), 5.42 (s, 2H, CH2), 2.18 (s, 3H,
CH3), 2.13 (s, 6H, CH3). 13C NMR (100 MHz, CDCl3): δ = 149.8 (s), 141.4 (s), 139.0 (s), 134.9 (s),
130.7 (s), 129.4 (d), 128.6 (d), 128.2 (d), 128.2 (d), 127.9 (d), 127.8 (d), 126.9 (d), 125.6 (s), 120.1
(s), 52.7 (t), 23.6 (q), 20.8 (q). FTIR (KBr): 2918, 1456, 1422, 1398, 1234 cm-1. HRMS: m/z [M]+
calcd for C24H23N3Se: 433.1057. Found: 433.1055.
1-{2-[(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)selanyl]phenyl}-N,N-dimethylmethanamine (4j)
1
156 mg (70%), Yellow oil. Rf = 0.3 (hexane-AcOEt, 2 : 1). H NMR (400 MHz, CDCl3): δ = 8.04
(dd, J = 8.8, 1.5 Hz, 2H, Ar-H), 7.39-7.29 (m, 3H, Ar-H), 7.19-7.15 (m, 5H, Ar-H), 7.11 (d, J = 6.3
Hz, 1H, Ar-H), 7.02 (td, J = 7.3, 1.0 Hz, 1H, Ar-H), 6.81 (td, J = 7.3, 1.5 Hz, 1H, Ar-H), 6.52 (d, J =
13
7.8 Hz, 1H, Ar-H), 5.57 (s, 2H, CH2), 3.49 (s, 2H, CH2), 2.23 (s, 6H, CH3). C NMR (100 MHz,
CDCl3): δ = 151.5 (s), 138.5 (s), 135.1 (s), 133.2 (s), 131.2 (s), 129.4 (d), 129.2 (d), 128.4 (d), 128.3
(d), 128.1 (d), 127.91 (d), 127.88 (d), 127.2 (d), 126.0 (d), 121.9 (s), 64.3 (t), 53.0 (t), 43.9 (q). FTIR
(neat): 2781, 1464, 1456, 1435, 1364 cm-1. HRMS: m/z [M]+ calcd for C24H24N4Se: 448.1166. Found:
448.1170.
2-[(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)selanyl]-N-(p-tolyl)benzamide (4k)
15
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
169 mg (65%), Colorless needle. Mp 222-222.5 °C (CH2Cl2 / hexane); Rf = 0.5 (hexane-AcOEt, 5 :
1). 1H NMR (400 MHz, CDCl3): δ = 8.05 (dd, J = 8.3, 1.5 Hz, 2H, Ar-H), 7.91 (s, 1H, NH), 7.64 (dd,
J = 7.8, 1.0 Hz, 1H, Ar-H), 7.54 (d, J = 8.8 Hz, 2H, Ar-H), 7.36-7.26 (m, 3H, Ar-H), 7.24-7.09 (m,
8H, Ar-H), 6.96 (td, J = 8.3, 1.2 Hz, 1H, Ar-H), 6.43 (dd, J = 8.3, 1.0 Hz, 1H, Ar-H), 5.65 (s, 2H,
CH2), 2.36 (s, 3H, CH3). 13C NMR (100 MHz, CDCl3): δ = 165.7 (s), 152.1 (s), 135.0 (s), 134.71 (s),
134.67 (s), 132.2 (d), 131.5 (s), 130.7 (s), 129.7 (d), 129.1 (d), 128.5 (d), 128.4 (d), 128.2 (d), 128.0
(d), 127.2 (d), 126.9 (d), 125.9 (d), 120.7 (d), 120.0 (s), 53.1 (t), 20.9 (q). FTIR (KBr): 3335, 1645,
1595, 1529, 1323 cm-1. HRMS: m/z [M]+ calcd for C29H24N4OSe: 524.1115. Found: 524.1112.
1-Benzyl-4-phenyl-5-(thiophen-2-ylselanyl)-1H-1,2,3-triazole (4l)
133 mg (67%), Colorless needle. Mp 120.5-122 °C (CH2Cl2 / hexane); Rf = 0.4 (hexane-AcOEt, 4 :
1). 1H NMR (400 MHz, CDCl3): δ = 8.04 (dd, J = 7.8, 1.5 Hz, 2H, Ar-H), 7.44 (t, J = 7.3 Hz, 2H, Ar-
H), 7.40-7.23 (m, 7H, Ar-H), 6.87 (d, J = 3.9 Hz, 1H, Ar-H), 6.79 (t, J = 5.4 Hz, 1H, Ar-H), 5.75 (s,
2H, CH2). 13C NMR (100 MHz, CDCl3): δ = 150.7 (s), 135.1 (s), 134.6 (d), 131.1 (d), 130.6 (s), 128.8
(d), 128.6 (d), 128.4 (d), 128.2 (d), 127.9 (d), 127.8 (d), 127.6 (d), 121.8 (s), 119.7 (s), 53.1 (t). FTIR
(KBr): 3028, 1472, 1454, 1337, 1219 cm-1. HRMS: m/z [M]+ calcd for C19H15N3SSe: 397.0152.
Found: 397.0151.
5-(Benzo[b]thiophen-2-ylselanyl)-1-benzyl-4-phenyl-1H-1,2,3-triazole (4m)
122 mg (60%), Colorless needle. Mp 137-139 °C (CH2Cl2 / hexane); Rf = 0.5 (hexane-AcOEt, 3 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.02 (dd, J = 8.3, 1.5 Hz, 2H, Ar-H), 7.62 (dd, J = 7.3, 1.0 Hz, 1H,
Ar-H), 7.53 (dd, J = 6.8, 2.9 Hz, 1H, Ar-H), 7.47-7.37 (m, 3H, Ar-H), 7.30-7.19 (m, 7H, Ar-H), 7.01
13
(s, 1H, Ar-H), 5.75 (s, 2H, CH2). C NMR (100 MHz, CDCl3): δ = 151.3 (s), 142.4 (s), 139.5 (s),
135.0 (s), 130.4 (s), 129.4 (d), 128.70 (s), 128.68 (d), 128.5 (d), 128.2 (d), 127.8 (d), 127.6 (d), 125.4
(s), 124.8 (d), 124.6 (d), 123.2 (d), 121.7 (d), 118.2 (s), 53.3 (t). FTIR (KBr): 1495, 1454, 1427, 1343,
1223 cm-1. HRMS: m/z [M]+ calcd for C23H17N3SSe: 447.0308. Found: 447.0308.
16
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
1-Benzyl-5-(benzylselanyl)-4-phenyl-1H-1,2,3-triazole (4n)
77 mg (38%), Colorless needle. Mp 90-91.5 °C (CH2Cl2 / hexane); Rf = 0.4 (hexane-AcOEt, 4 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.07 (dd, J = 8.3, 1.5 Hz, 2H, Ar-H), 7.45-7.10 (m, 11H, Ar-H),
13
6.83 (dd, J = 6.6, 2.9 Hz, 2H, Ar-H), 5.32 (s, 2H, CH2), 3.59 (s, 2H, CH2). C NMR (100 MHz,
CDCl3): δ = 150.8 (s), 136.9 (s), 135.5 (s), 130.8 (s), 128.8 (d), 128.62 (d), 128.57 (d), 128.4 (d),
128.3 (d), 128.2 (d), 127.8 (d), 127.5 (d), 127.2 (d), 118.1 (s), 52.5 (t), 33.3 (t). FTIR (KBr): 1495,
1458, 1429, 1340, 1217 cm-1. HRMS: m/z [M]+ calcd for C22H19N3Se: 405.0744. Found: 405.0747.
1-Benzyl-4-(4-methoxyphenyl)-5-(phenylselanyl)-1H-1,2,3-triazole (4o)
158 mg (75%), Colorless plate. Mp 96-97 °C (Et2O); Rf = 0.3 (hexane-AcOEt, 4 : 1). 1H NMR (400
MHz, CDCl3): δ = 7.98 (d, J = 9.2 Hz, 2H, Ar-H), 7.22-7.16 (m, 5H, Ar-H), 7.16-7.08 (m, 3H, Ar-H),
13
6.98-6.90 (m, 4H, Ar-H), 5.64 (s, 2H, CH2), 3.82 (s, 3H, CH3). C NMR (100 MHz, CDCl3): δ =
159.9 (s), 151.5 (s), 134.9 (s), 129.73 (s), 129.67 (d), 129.1 (d), 128.8 (d), 128.6 (d), 128.2 (d), 127.9
(d), 127.1 (d), 123.0 (s), 116.9 (s), 113.9 (d), 55.2 (q), 53.1 (t). FTIR (KBr): 1539, 1478, 1456, 1260,
1245 cm-1. HRMS: m/z [M]+ calcd for C22H19N3OSe: 421.0693. Found: 421.0690.
1-Benzyl-5-(phenylselanyl)-4-(p-tolyl)-1H-1,2,3-triazole (4p)
135 mg (73%), Colorless plate. Mp 79-81 °C (Et2O); Rf = 0.3 (hexane-AcOEt, 5 : 1). 1H NMR (400
MHz, CDCl3): δ = 7.93 (d, J = 8.3 Hz, 2H, Ar-H), 7.24-7.16 (m, 7H, Ar-H), 7.16-7.08 (m, 3H, Ar-H),
13
6.96 (dd, J = 7.8, 1.5 Hz, 2H, Ar-H), 5.64 (s, 2H, CH2), 2.36 (s, 3H, CH3). C NMR (100 MHz,
CDCl3): δ = 151.7 (s), 138.5 (s), 134.8 (s), 129.7 (s), 129.6 (d), 129.2 (d), 129.1 (d), 128.6 (d), 128.1
(d), 127.9 (d), 127.6 (s), 127.3 (d), 127.1 (d), 117.3 (s), 53.1 (t), 21.3 (q). FTIR (KBr): 1576, 1478,
1456, 1439, 1335 cm-1. HRMS: m/z [M]+ calcd for C22H19N3Se: 405.0744. Found: 405.0742.
1-Benzyl-5-(phenylselanyl)-4-[4-(trifluoromethyl)phenyl]-1H-1,2,3-triazole (4q)
167 mg (73%), Colorless needle. Mp 112-114 °C (CH2Cl2 / hexane); Rf = 0.3 (hexane-AcOEt, 5 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.19 (d, J = 8.3 Hz, 2H, Ar-H), 7.64 (d, J = 8.8 Hz, 2H, Ar-H), 7.26-
17
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
7.09 (m, 8H, Ar-H), 6.96 (dd, J = 7.8, 1.0 Hz, 2H, Ar-H), 5.68 (s, 2H, CH2). 13C NMR (100 MHz,
2
CDCl3): δ = 150.0 (s), 134.6 (s), 134.0 (s), 130.0 (s, JC,F = 32 Hz), 129.8 (d), 129.3 (d), 129.1 (s),
128.7 (d), 128.3 (d), 127.6 (d), 127.55 (d), 127.53 (d), 125.4 (d, 3JC,F = 3.3 Hz), 124.1 (s, 1JC,F = 271
Hz), 118.8 (s), 53.3 (t). FTIR (KBr): 1559, 1497, 1456, 1417, 1234 cm-1. HRMS: m/z [M]+ calcd for
C22H16F3N3Se: 459.0462. Found: 459.0465.
1-Benzyl-4-(cyclohex-1-en-1-yl)-5-(phenylselanyl)-1H-1,2,3-triazole (4r)
145 mg (74%), Yellow oil. Rf = 0.3 (hexane-AcOEt, 5 : 1). 1H NMR (400 MHz, CDCl3): δ = 7.22-
7.11 (m, 8H, Ar-H), 6.96 (dd, J = 8.3, 2.0 Hz, 2H, Ar-H), 6.47-6.45 (m, 1H, cyclohexene), 5.58 (s,
2H, CH2), 2.58-2.54 (m, 2H, cyclohexene), 2.17-2.11 (m, 2H, cyclohexene), 1.73-1.69 (m, 2H,
cyclohexene), 1.63-1.58 (m, 2H, cyclohexene). 13C NMR (100 MHz, CDCl3): δ = 153.4 (s), 135.0 (s),
130.1 (s), 129.5 (d), 129.2 (d), 129.0 (d), 128.6 (d), 128.1 (s), 128.0 (d), 127.8 (d), 127.0 (d), 116.6
(s), 52.9 (t), 27.0 (t), 25.6 (t), 22.6 (t), 21.9 (t). FTIR (neat): 1576, 1497, 1478, 1437, 1323 cm-1.
HRMS: m/z [M]+ calcd for C21H21N3Se: 395.0901. Found: 395.0902.
1-Benzyl-4-butyl-5-(phenylselanyl)-1H-1,2,3-triazole[13] (4s)
154 mg (83%), Yellow oil. Rf = 0.4 (hexane-AcOEt, 4 : 1). 1H NMR (400 MHz, CDCl3): δ = 7.23-
7.10 (m, 8H, Ar-H), 6.96 (dd, J = 8.3, 1.0 Hz, 2H, Ar-H), 5.57 (s, 2H, CH2), 2.72 (t, J = 7.8 Hz, 2H,
CH2), 1.63 (quit, J = 7.7 Hz, 2H, CH2), 1.32 (sext, J = 7.4 Hz, 2H, CH2), 0.87 (t, J = 7.3 Hz, 3H, CH3).
13C NMR (100 MHz, CDCl3): δ = 154.2 (s), 135.0 (s), 129.7 (d), 129.6 (s), 129.5 (d), 128.6 (d), 128.1
(d), 127.9 (d), 127.2 (d), 119.1 (s), 53.1 (t), 31.4 (t), 25.6 (t), 22.4 (t), 13.7 (q). HRMS: m/z [M]+ calcd
for C19H21N3Se: 371.0901. Found: 371.0905.
1-Cinnamyl-4-phenyl-5-(phenylselanyl)-1H-1,2,3-triazole (4t)
119 mg (57%), Colorless oil. Rf = 0.3 (hexane-AcOEt, 4 : 1). 1H NMR (400 MHz, CDCl3): δ = 8.07
(d, J = 6.8 Hz, 2H, Ar-H), 7.44-7.34 (m, 4H, Ar-H), 7.24-7.12 (m, 9H, Ar-H), 6.49 (d, J = 15.6 Hz,
1H, -CH=CH-), 6.22-6.14 (m, 1H, -CH=CH-), 5.24 (d, J = 6.3 Hz, 2H, CH2). 13C NMR (100 MHz,
18
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
CDCl3): δ = 135.7 (s), 134.8 (d), 130.6 (s), 129.83 (d), 129.76 (s), 129.5 (d), 128.6 (d), 128.49 (d),
128.46 (d), 128.2 (d), 127.5 (d), 127.4 (d), 126.6 (d), 122.2 (d), 51.6 (t). FTIR (neat): 3057, 1576,
1476, 1449, 1439 cm-1. HRMS: m/z [M]+ calcd for C23H19N3Se: 417.0744. Found: 417.0747.
Ethyl 2-{4-phenyl-5-(phenylselanyl)-1H-1,2,3-triazol-1-yl}acetate (4u)
100 mg (52%), Colorless plate. Mp 80.5-81.5 °C (AcOEt / hexane); Rf = 0.3 (hexane- AcOEt, 4 : 1).
1H NMR (400 MHz, CDCl3): δ = 8.10-8.07 (m, 2H, Ar-H), 7.44-7.34 (m, 3H, Ar-H), 7.22-7.14 (m,
5H, Ar-H), 5.24 (s, 2H, CH2), 4.12 (q, 2H, J = 7.2 Hz, CH2), 1.21 (t, 3H, J = 7.1 Hz, CH3). 13C NMR
(100 MHz, CDCl3): δ = 166.1 (s), 151.1 (s), 130.3 (s), 129.8 (d), 128.9 (s), 128.6 (d), 128.5 (d), 127.6
(d), 127.4 (d), 118.9 (s), 62.3 (t), 50.3 (t), 14.0 (q). FTIR (KBr): 3024, 1750, 1554, 1478, 1248 cm-1.
HRMS: m/z [M]+ calcd for C18H17N3O2Se: 387.0486. Found: 387.0488.
1-(Naphthalen-1-ylmethyl)-4-phenyl-5-(phenylselanyl)-1H-1,2,3-triazole (4v)
137 mg (62%), Colorless plate. Mp 126.5-128.0 °C (AcOEt / hexane); Rf = 0.4 (hexane- AcOEt, 4 :
1). 1H NMR (400 MHz, CDCl3): δ = 8.15 (d, 1H, J = 7.8 Hz, Ar-H), 8.08 (d, 2H, J = 7.3 Hz, Ar-H),
7.83 (dd, 1H, J = 7.8, 2.0 Hz, Ar-H), 7.72 (d, 1H, J = 8.3 Hz, Ar-H), 7.56-7.47 (m, 2H, Ar-H), 7.42-
7.32 (m, 3H, Ar-H), 7.23 (t, 1H, J = 8.3 Hz, Ar-H), 7.12-7.00 (m, 4H, Ar-H), 6.93 (d, 2H, J = 8.3 Hz,
Ar-H), 6.12 (s, 2H, CH2). 13C NMR (100 MHz, CDCl3): δ = 151.5 (s), 133.6 (s), 130.7 (s), 130.5 (s),
130.4 (s), 129.5 (d), 129.4 (s), 129.3 (d), 128.9 (d), 128.8 (d), 128.6 (d), 128.5 (d), 127.5 (d), 127.2
(d), 126.7 (d), 126.4 (d), 126.0 (d), 125.1 (d), 122.9 (d), 118.3 (s), 51.0 (t). FTIR (KBr): 3055, 1576,
1476, 1441, 1339 cm-1. HRMS: m/z [M]+ calcd for C25H19N3Se: 441.0744. Found: 441.0741.
4-Phenyl-5-(phenylselanyl)-1-{(phenylthio)methyl}-1H-1,2,3-triazole (4w)
125 mg (59%), Yellow oil. Rf = 0.4 (hexane-AcOEt, 4 : 1). 1H NMR (400 MHz, CDCl3): δ = 8.04 (d,
13
2H, J = 8.3 Hz, Ar-H), 7.41-7.25 (m, 8H, Ar-H), 7.20-7.08 (m, 5H, Ar-H), 5.71 (s, 2H, CH2). C
NMR (100 MHz, CDCl3): δ = 151.2 (s), 132.9 (d), 132.1 (s), 130.2 (s), 129.7 (d), 129.5 (d), 129.4 (s),
129.2 (d), 128.6 (d), 128.4 (d), 127.5 (d), 127.3 (d), 117.8 (s), 53.5 (t). FTIR (neat): 1559, 1506, 1474,
19
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
1439, 1341 cm-1. HRMS: m/z [M]+ calcd for C21H17N3SSe: 423.0308. Found: 423.0310.
Acknowledgements
This research was supported by a research grant from Nagai Memorial Research Scholarship from
the Pharmaceutical Society of Japan. The authors also thank Institute of Pharmaceutical Life Sciences,
Aichi Gakuin University, and Hokuriku University for generous financial support.
References
[1] a) T. Wirth, Organoselenium Chemistry, Wiley-VCH, Weinheim, 2012; b) A. Ogawa, Main
Group Metals in Organic Synthesis Vol. 2; H. Yamamoto, K. Oshima, Ed., Wiley-VCH:
Weinheim, 2004, Chap. 15, 813–831; c) S. Santoro, J. B. Azeredo, V. Nascimento, L. Sancineto,
A. L. Braga, C. Santi, RSC Adv. 2014, 4, 31521–31535; d) S. T. Manjare, Y. Kim, D. G.
Churchill, Acc. Chem. Res. 2014, 47, 2985–2998; e) F. Marini, S. Sternativo, Synlett 2013, 24,
11–19; f) A. J. Mukherjee, S. S. Zade, H. B. Singh, R. B. Sunoj, Chem. Rev. 2010, 110, 4357–
4416; g) D. M. Freudendahl, S. A. Shahzad, T. Wirth, Eur. J. Org. Chem. 2009, 1649–1664.
[2] a) C. W. Nogueira, J. B. T. Rocha, Arch. Toxicol. 2011, 85, 1313–1359; b) B. K. Sarma, G.
Mugesh, Org. Biomol. Chem. 2008, 6, 965–974; c) C. W. Nogueira, G. Zeni, J. B. T. Rocha,
Chem. Rev. 2004, 104, 6255–6285; d) G. Mugesh, W. -W. Mont, H. Sies, Chem. Rev. 2001,
101, 2125–2179.
[3] a) E. A. Santos, E. Hamel, R. Bai, J. C. Burnett, C. S. S. Tozatti, D. Bogo, R. T. Perdomo, A.
M. M. Antunes, M. M. Marques, M. F. C. Matos, D. P. Lima, Bioorg. Med. Chem. Lett. 2013,
23, 4669–4673; b) L. Engman, I. Cotgreave, M. Angulo, C. W. Taylor, G. D. Paine-Murriet, G.
Powis, Anticancer Res. 1997, 17, 4599–4605; c) L. Engman, D. Stern. H. Frisell, K. Vessman,
M. Berglund, B. Ek, C.-M. Andersson, Bioorg. Med. Chem. 1995, 3, 1255–1262; d) C.-M.
Andersson, A. Hallberg, M. Linden, R. Brattsand, P. Moldéus, I. Cotgreave, Free Radical Biol.
Med. 1994, 16, 17–28; f) J. A. Woods, J. A. Hadfield, A. T. McGown, B. W. Fox, Bioorg. Med.
Chem. 1993, 1, 333–340; g) N. M. Goudgaon, F. N. M. Naguib, M. H. Kouni, R. F. Schinazi,
20
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
J. Med. Chem. 1993, 36, 4250–4254.
[4] L. Savegnago, A. I. Vieira, N. Seus, B. S. Goldani, M. R. Castro, E. J. Lenardão, D. Alves,
Tetrahedron Lett. 2013, 54, 40–44.
[5] R. L. Grange, J. Ziogas, J. A. Angus, C. H. Schiesser, Tetrahedron Lett. 2007, 48, 6301–6303.
[6] B. M. Gai, C. F. Bortolatto, S. O. Heck, A. L. Stein, M. M. M. F. Duarte, G. Zeni, C. W.
Nogueira, Psychopharmacology 2014, 231, 2119–2130.
[7] a) B. C. Ranu, R. Dey, T. Chatterjee, S. Ahammed, ChemSusChem 2012, 5, 22–44; b) I. P.
Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596–1636; c) I. P. Beletskaya, V. P.
Ananikov, Catalyzed Carbon-Heteroatom Bond Formation; A. K. Yudin, Ed., Wiley-VCH:
Weinheim, 2011, Chap. 3, 69–118; d) J. X. Qiao, P. Y. S. Lam, Synthesis 2011, 829–856; e) I.
P. Beletskaya, V. P. Ananikov, Eur. J. Org. Chem. 2007, 3431–3444.
[8] a) N. Taniguchi, T. Onami, Synlett 2003, 829–832; b) N. Taniguchi, T. Onami, J. Org. Chem.
2004, 69, 915–920; c) S. Kumar, L. Engman, J. Org. Chem. 2006, 71, 5400–5403; d) V. P.
Reddy, A. V. Kumar, K. Swapna, K. R. Rao, Org. Lett. 2009, 11, 951–953; e) D. Singh, E. E.
Alberto, O. E. D. Rodrigues, A. L. Braga, Green Chem. 2009, 11, 1521–1524; f) Y. Li, H. Wang,
X. Li, T. Chen, D. Zhao, Tetrahedron 2010, 66, 8583–8586; g) K. Swapna, S. N. Murthy, Y.
V. D. Nageswar, Eur. J. Org. Chem. 2011, 1940–1946; h) A. Dandapat, C. Korupalli, D. J. C.
Prasad, R. Singh, G. Sekar, Synthesis 2011, 2297–2302; i) T. Chatterjee, B. C. Ranu, J. Org.
Chem. 2013, 78, 7145–7153; j) B. Movassagh, Z. Hosseinzadeh, Synlett 2016, 777–781.
[9] a) L. Wang, M. Wang, F. Huang, Synlett 2005, 2007–2010; b) N. Taniguchi, J. Org. Chem.
2007, 72, 1241–1245; c) D. Alves, C. G. Santos, M. W. Paixão, L. C. Soares, D. Souza, O. E.
D. Rodrigues, A. L. Braga, Tetrahedron Lett. 2009, 50, 6635–6638; d) V. G. Ricordi, C. S.
Freitas, G. Perin, E. J. Lenardão, R. G. Jacob, L. Savegnago, D. Alves, Green Chem. 2012, 14,
1030–1034; e) B. Zheng, Y. Gong, H.-J. Xu, Tetrahedron 2013, 69, 5342–5347; f) A. Kumar,
S. Kumar, Tetrahedron 2014, 70, 1763–1772; g) S. Roy, T. Chatterjee, S. M. Islam,
Tetrahedron Lett. 2015, 56, 779–783.
21
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
[10] M. Matsumura, K. Shibata, S. Ozeki, M. Yamada, Y. Murata, N. Kakusawa, S. Yasuike,
Synthesis 2016, 48, 730–736.
[11] a) L. Ackermann, H. K. Potukuchi, Org. Biomol. Chem. 2010, 8, 4503–4513; b) S. G. Agalave,
S. R. Maujan, V. S. Pore, Chem. Asian J. 2011, 6. 2696–2718.
[12] V. Malnuit, M. Duca, A. Manout, K. Bougrin, R. Benhida, Synlett 2009, 2123–2128.
[13] S. Ding, G. Jia, J. Sun, Angew. Chem. Int. Ed. 2014, 53, 1877–1880.
[14] W. Wang, X. Peng, F. Wei, C.-H. Tung, Z. Xu, Angew. Chem. Int. Ed. 2016, 55, 649–653.
[15] G. Cera, L. Ackermann, Chem. Eur. J. 2016, 22, 8475–8478.
[16] M. Yamada, M. Matsumura, Y. Uchida, M. Kawahata, Y. Murata, N. Kakusawa, K. Yamaguchi,
S. Yasuike, Beilstein J. Org. Chem. 2016, 12, 1309–1313.
[17] a) M. Yamada, M. Matsumura, M. Kawahata, Y. Murata, N. Kakusawa, K. Yamaguchi, S.
Yasuike, J. Organomet. Chem. 2017, 834, 83–87; b) M. Yamada, M. Matsumura, Y. Murata,
M. Kawahata, K. Saito, N. Kakusawa, K. Yamaguchi, S. Yasuike, Tetrahedron 2017, 73, 2614–
2622.
[18] N. Kakusawa, K. Yamaguchi, J. Kurita, J. Organomet. Chem. 2005, 690, 2956-2966.
[19] a) V. G. Ricordi, S. Thurow, F. Penteado, R. F. Schumacher, G. Perin, E. J. Lenardão, D. Alves,
Adv. Synth. Catal. 2015, 357, 933–939; b) A. L. Stein, F. N. Bilheri, J. T. Rocha, D. F. Back,
G. Zeni, Chem. Eur. J. 2012, 18, 10602–10608; c) I. P. Beletskaya, A. S. Sigeev, A. S.
Peregudov, P.V. Petrovskii, V. N. Khrustalev, Chem. Lett. 2010, 39, 720–722.
[20] R. B. Miller, G. McGarvey, J. Org. Chem. 1978, 43, 4424–4431.
[21] H. A. Stefani, S. N. S. Vasconcelos, F. Manarin, D. M. Leal, F. B. Souza, L. S. Madureira, J.
Zukerman-Schpector, M. N. Eberlin, M. N. Godoi, R. S. Galaverna, Eur. J. Org. Chem. 2013,
3780–3785.
[22] L. S. Campbell-Verduyn, L. Mirfeizi, R. A. Dierckx, P. H. Elsinga, B. L. Feringa, Chem
Commun. 2009, 2139–2141.
[23] T. Suzuki, Y. Ota, M. Ri, M. Bando, A. Gotoh, Y. Itoh, H. Tsumoto, P. R. Tatum, T. Mizukami,
22
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
H. Nakagawa, S. Iida, R. Ueda, K. Shirahige, N. Miyata, J. Med. Chem. 2012, 55, 9562–9575.
[24] Z. Li, F. Ke, H. Deng, H, Xu, H. Xiang, X. Zhou, Org. Biomol. Chem. 2013, 11, 2943–2946.
[25] H. Poleschner, M. Heydenreich, U. Schilde, Liebigs Ann. 1996, 1187–1193.
[26] T. Arnauld, D. H. R. Barton, J.-F. Normant, J. Org. Chem. 1999, 64, 3722–3725.
[27] K. Hiroi, S. Sato, Synthesis 1985, 635–638.
[28] H. Poleschner, K. Seppelt, Chem. Eur. J. 2004, 10, 6565–6574.
[29] N. Stuhr-Hansen, T. I. Sølling, L. Henriksen, Tetrahedron 2011, 67, 2633–2643.
[30] T. Yamamoto, S. Ogawa, R. Sato, Chem. Lett. 2006, 35, 422–423.
23
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201701389
European Journal of Organic Chemistry
Graphical abstract
Short text
Cu-catalyzed three-component reaction of ethynylstibanes, organic azides, and diaryl diselenides
under aerobic conditions led to the formation of fully substituted 5-selanyl-1,2,3-triazoles in moderate
to excellent yields. Ethynylstibanes having antimony atom gave superior results compared to various
alkynes having other typical elements such as silicon, tin, and tellurium.
Key Topic
Three-component reaction
Reaction of organoantimony
24
This article is protected by copyright. All rights reserved.