Metal-Free Synthesis of Etherified 3-(1H-1,2,3-Triazol-1-yl)phenyl Iodides through O–H Arylation/C–H Iodination with Diacetoxyiodobenzenes

Article abstract of DOI:10.1002/ejoc.201701114

A concise and efficient method for the synthesis of etherified 3-(1H-1,2,3-triazol-1-yl)phenyl iodides from 1,4-disubstituted 1,2,3-triazoles under metal-free conditions has been developed. In the presence of ArI(OAc)₂, a range of 1,2,3-triazole substrates that contain a hydroxy group underwent a direct O–H arylation and C–H iodination to afford functionalized 1,2,3-triazoles in good to excellent yields.

Full text of DOI:10.1002/ejoc.201701114

A Journal of
Accepted Article
Title: Metal-free synthesis of etherfied 1, 2, 3-triazole idodides through
O-H arylation / C-H iodation with diacetoxyiodobenzenes
Authors: Yaowen Liu, Jianhua Yang, Xinyuan Ma, Chunmei Han, and
Yubo Jiang
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.201701114
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701114
Supported by

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
Metal-free synthesis of etherfied 1, 2, 3-triazole idodides through
O-H arylation / C-H iodation with diacetoxyiodobenzenes
[a]
[a]
[a]
[a]
[a]
Yaowen Liu, Jianhua Yang, Xinyuan Ma, Chunmei Han, and Yubo Jiang*
Dedication ((optional))
[
16]
Abstract: An efficient method for the synthesis of etherfied 1, 2, 3-
triazoles is highly desirable. In the past few years, Kuang, Shi
and Ackermann groups respectively explored various
modifications of 2-monosubstituted 1, 2, 3-triazoles including
halogenation, arylation, alkoxylation, acylation, and acyloxylation,
triazole idodides from 1, 4-disubstituted 1, 2, 3-triazoles under metal
2
free conditions has been developed. In the presence of ArI(OAc) , a
range of 1, 2, 3-triazole substrates bearing hydroxyl group undergo
the direct O-H arylation and C-H iodation simultaneously to
accomplish the modification of the 1, 2, 3-triazoles. This method
provides a concise and efficient pathway to synthesize highly
functionalized 1, 2, 3-triazole derivatives in good to excellent yields.
[
17]
generating corresponding functionalized target molecules.
These methods have been proved to have good potential but
are mainly limited to the mono-substituted-1, 2, 3-triazoles.
Recently, our group explored direct modification of 1, 4-
disubstituted 1, 2, 3-triazoles, as a beautiful means for the
construction of various 1, 2, 3-triazoles with complicated
structures and respectively achieved C-H bond arylation,
acylation, and acyloxylation, through the influence of the triazole
Introduction
[
18]
ring. The aryloxylation process was also acheived by Ullmann
C–O coupling, generating series of etherfied 1, 2, 3-
1, 2, 3-Triazoles are important five-membered heterocyclic
a
scaffolds, which were widely applied in various fields such as
[19]
[20]
triazoles. With respect to the C-H halogenations, Liu group
reported the copper-catalyzed and mediated C–X (X = F, Cl, Br,
I) bond formation via direct C–H bond transformation. To the
best of our knowledge, there is still no report on the metal-free
synthesis of etherfied 1, 2, 3-triazole idodides. Herein, we would
like to report a convenient method for metal-free synthesis of
etherfied 1, 2, 3-triazole idodides from 1, 4-diaryl 1, 2, 3-triazoles
bearing hydroxyl group, in which direct O-H arylation and C-H
[
1]
[2]
[3]
organic synthesis, materials, medicinal chemistry and food
[
4]
additives due to their extensive biological activities. It may
display a wide spectrum of biological activities such as anti-
[
5]
[6]
[7]
[8]
[9]
HIV, anticancer, antiviral, antifungal, antimicrobial, and
[
10]
antibacterial activities,
although the 1, 2, 3-triazole structure
was not found in natural products. Numerous compounds
bearing this moiety are also well acknowledged for therapeutic
effects elucidated in Fig. 1
2
iodation occurred simultaneously in the presence of ArI(OAc) .
Results and Discussion
Our initial studies focused on the model reaction of 2-(4-(p-tolyl)-
H-1, 2, 3-triazol-1-yl) phenol 1a and diacetoxyiodobenzene
DAIB) 2a. We investigated the effects of catalyst, oxidant,
solvent and temperature respectively, as summarized in Table 1.
moderate 61% yield of the product 1-(3-iodo-2-
1
(
Fig.1. Triazole containing commercial drugs and bioactive molecules.
Owing to these widely applications, the development of facile
synthesis and modification of 1, 2, 3-triazole compounds
therefore strongly attracted enormous interests. Numerous
methods for the preparation of 1, 2, 3-triazole derivatives have
been developed in the last decades. Among them, the landmark
discovery of the alkyne-azide cycloaddition (AAC) reactions
A
phenoxyphenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole 3a was obtained
when the reaction was catalyzed by CuCl (0.1 equiv.), using 2
◦
equiv. of PhI(OAc)
2
in solvent of PhMe under 120 C for 12h
(
Table 1, entry 1). The molecular structure of 3a was
unambiguously confirmed by a single crystal X-ray diffraction
study (Table 1). Catalyst screening demonstrated that PdCl was
the best choice, in which a good yield of 65% was obtained
entries 1–7). However, other catalysts such as CuBr, CuCl
NiCl , CoCl , and AgNO are not so efficient for this reaction
Table 1, entries 2, 3, 5, 6 and 7). To our delight, a good 67%
yield was also reached in the absence of the catalyst (Table 1,
[
11]
[12]
[13]
disclosed by Huisgen,
Sharpless,
and Meldal,
respectively, reached unprecedented sophistication and height.
[
14]
2
Other partners such as activated carbonyl compounds and
[
15]
activated alkenes
were also involved for this purpose.
(
2
,
However, most traditional methodologies still met some troubles
for the target molecules with complicated structures. It is clear
that the development of new accesses for various 1, 2, 3-
2
2
3
(
entry 8). Next, to gain the ideal yield, the amount of PhI(OAc)
was examined and it turned out that 3.5 equiv of PhI(OAc)
could bring a yield of 73% and increasing the amount of DAIB to
4 equiv could not raise the yield evidently (Table 1, entries 9-11).
2
2
[
a]
Initial(s), Surname(s) of Author(s) including Corresponding Author(s)
Department: Faculty of Science
Institution: Kunming University of Science and Technology
Address: Jingming South Road 727, Kunming 650500, China
E-mail: ybjiang@kmust.edu.cn
Then, various solvents including CH
dioxane were also screened, indicating that CH
3
CN, DCE, DMF, and
CN was the best
3
Supporting information for this article is given via a link at the end of
the document. ((Please delete this text if not appropriate))
choice (entries 12–15). Additionally, the yield can not be
improved when the reaction temperature was adjusted to lower
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
◦
◦
◦
8
0 C, 100 C or a higher 130 C, respectively (Table 1, entries
yields (Table 2, 3f-3j). The substituent on C-4 aryl of 1, 2, 3-
16–18). After further optimizations, the best result was obtained
triazoles seems to have an obvious effect on the reactions. The
a,b
a,b
Table 1. Selected optimization of the reaction conditions.
Table 2. Scope of 1, 4-disubstituted 1, 2, 3-triazoles.
Entry
Catalyst
mol %)
DAIB
(Equiv.)
Solvent
Temp.
( C)
Yield
[%]
o
[b]
(
1
2
3
4
5
6
7
8
9
CuCl (10)
CuBr (10)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
3.0
3.5
4.0
3.5
3.5
3.5
3.5
3.5
3.5
3.5
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
PhMe
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
80
61
52
55
65
50
49
63
67
69
73
70
78
63
55
59
53
62
75
CuCl
PdCl
2
(10)
2
(10)
NiCl
2
(10)
CoCl
2
(10)
3
AgNO (10)
--
--
--
--
--
--
--
--
--
--
--
10
11
12
13
14
15
16
17
18
3
CH CN
a
Reaction conditions: 1, 4-disubstituted 1, 2, 3-triazoles 1 (0.3 mmol) and
DCE
DMF
diacetoxyiodobenzenes (1.05 mmol) were added to CH
3
CN (2 mL) and
o
b
stirred at 120
chromatography.
C for 12 h.
Yield of isolated product after column
dioxane
3
substrates with a substituent (-CH , -OMe and -Cl) on meta or
ortho position produced only lower yields in comparison with
those bearing a group at the para position, probably owning to
the steric effects (Table 2, 3a vs. 3c, 3d vs. 3e, 3f and 3g vs.
CH
CH
CH
3
CN
3
CN
3
CN
100
130
3h). It should be noted that C-4 pyridyl substrate was also
tolerated in the system and good yield was also obtained (3k).
Moreover, when the 1, 2, 3-triazoles has hydroxyl group on ortho
position of C-4 aryl or para position of N-1 aryl, good yields were
achieved (3l, 3m). Additionally, we checked 4-nitrophenol in this
system, which could also delivered the desired products in good
yield (3n).
Next, we turned our attention to investigate the scope of the
diacetoxyiodobenzenes, which were summarized in Table 3.
The reactions of 2-(4-(p-tolyl)-1H-1, 2, 3-triazol-1-yl) phenol 1a
and various diacetoxyiodobenzenes 2 went smoothly, affording
the products in moderate to good yields (Table 3, 3o-3s). The
substrates 2 with an electron-donating group (-Me) are inferior to
those bearing an electron-withdrawing group (-Br, -Cl) (3o and
a
Reaction conditions unless otherwise noted: 2-(4-(p-tolyl)-1H-1, 2, 3-triazol-1-
yl) phenol 1a (0.3 mmol) and diacetoxyiodobenzene 2a (3.5 eq.) were added
o
b
to solvent (2 mL) and stirred at 120 C for 12 h. Isolated yield.
◦
using a treatment of 3.5 equiv of DAIB in CH
h, which affording the desired etherfied 1, 2, 3-triazole idodide
3
3
CN at 120 C for 12
a in 78% yield (entry 14).
With the optimal conditions in hand, the scope of 1, 4-
disubstituted 1, 2, 3-triazoles
summarized in Table 2, the reaction of PhI(OAc)
-disubstituted 1, 2, 3-triazoles 1 bearing hydroxyl group on N-1
1
was firstly studied. As
2
with various 1,
4
aryl or C-4 aryl could proceed well and generate the desired
products 3 in good to excellent yields (3a-3n). The 1, 2, 3-
3p vs. 3q, 3r and 3s). Additionally, the steric results of the
triazole substrates with electron-donating groups (-CH
on C-4 aryl could react well and afford good yields (Table 2, 3a-
e), and those with an electron-withdrawing group (-Br, -Cl)
could also produce the desired compounds in moderate to good
3
, -OMe)
substituents are closely related to its electronic effect. Electron-
donating group on meta position are favorable for this
transformation (3p vs. 3o), while the electron withdrawing on
meta position are unfavorable for the reaction (3r vs. 3s).
3
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
Notably, no product was obtained, when the reaction was
disubstitued 1, 2, 3-triazoles monitored by TLC analysis, H O (15 mL)
2
conducted with PhI(OTFA)
2
.
was added to the mixture and extracted with EtOAc (3 × 25 mL). The
To gain a preliminary mechanistic insight into the reaction, a
control experiment was carried out. When 2, 2, 6, 6-tetramethyl-
combined organic layer was washed with brine (3 × 5 mL), dried with
2 4
Na SO , and concentrated under reduced pressure to afford the crude
1-piperidiny-loxy (TEMPO), as a radical inhibitor, was added into
product. Purification by column chromatography on silica gel with EtOAc /
a,b
Table 3. Scope of diacetoxyiodobenzenes.
PE (1:6) afforded the desired product 3.
1
-(3-iodo-2-phenoxyphenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole (3a): Yellow
o
1
solid (106 mg, 78% yield); Mp. 142.0-143.0 C; H NMR (400 MHz,
CDCl ) δ = 8.17 (s, 1H), 7.99 (ddd, J = 13.6, 8.0, 1.4 Hz, 2H), 7.63 (d, J =
.1 Hz, 2H), 7.21 (dt, J = 14.1, 4.8 Hz, 5H), 6.96 (t, J = 7.4 Hz, 1H), 6.74
3
8
13
(d, J = 7.9 Hz, 2H), 2.37 (s, 3H). C NMR (100 MHz, CDCl
3
) δ = 155.8,
1
1
47.9, 146.2, 140.5, 138.2, 131.6, 129.8, 129.5, 127.9, 127.2, 126.2,
+
25.7, 123.1, 120.5, 115.1, 93.3, 21.3. HRMS (ESI) m/z [M + H ]: calcd
for C21H17IN
3
O: 454.0416, found: 454.0418; IR (KBr): 3437, 3137, 2920,
-
1
1588, 1500, 1490, 1390, 1239, 1194, 1031, 872, 814, 742, 509 cm .
1
-(3-iodo-2-phenoxyphenyl)-4-phenyl-1H-1, 2, 3-triazole (3b): Yellow
o
1
solid (105 mg, 80% yield); Mp. 131.5-133.0 C; H NMR (400 MHz,
CDCl ) δ = 8.22 (s, 1H), 8.00 (ddd, J = 13.9, 8.0, 1.4 Hz, 2H), 7.79 – 7.71
(m, 2H), 7.41 (t, J = 7.5 Hz, 2H), 7.33 (t, J = 7.4 Hz, 1H), 7.21 (dd, J =
3
a
Reaction conditions: 2-(4-(p-tolyl)-1H-1, 2, 3-triazol-1-yl) phenol 1a (0.3
13
mmol) and diacetoxyiodobenzenes 2 (1.05 mmol) were added to CH
mL) and stirred at 120 C for 12 h. Yield of isolated product after column
chromatography.
3
CN (2
15.6, 7.7 Hz, 3H), 6.97 (t, J = 7.4 Hz, 1H), 6.74 (d, J = 7.9 Hz, 2H).
NMR (100 MHz, CDCl ) δ = 155.8, 147.8, 146.2, 140.5, 131.6, 130.1,
29.8, 128.8, 128.3, 127.9, 126.2, 125.8, 123.1, 120.9, 115.1, 93.3.
C
o
b
3
1
+
HRMS (ESI) m/z [M + H ]: calcd for C21
3
H15IN O: 440.0260, found:
the reaction under standard conditions, the yield was virtually
unaffected (Scheme 1). This result indicates that the reaction is
not a radical pathway.
4
1
40.0262; IR (KBr): 3440, 3136, 3051, 2924, 2855, 1757, 1671, 1586,
-
1
480, 1442, 1236, 1191, 1070, 1075, 904, 858, 764, 688, 506 cm .
1
-(3-iodo-2-phenoxyphenyl)-4-(m-tolyl)-1H-1, 2, 3-triazole (3c): Light
1
yellow oil (107 mg, 79% yield); H NMR (400 MHz, CDCl
3
) δ = 8.19 (s,
1
H), 7.99 (ddd, J = 16.6, 8.0, 1.5 Hz, 2H), 7.53 – 7.45 (m, 2H), 7.23 –
13
Scheme 1. Control Experiment.
7.12 (m, 5H), 6.94 (s, 1H), 6.74 (d, J = 7.9 Hz, 2H), 2.24 (s, 3H).
NMR (100 MHz, CDCl ) δ = 155.8, 147.9, 140.5, 138.5, 130.1, 129.8,
29.1, 128.7, 128.7, 127.8, 126.5, 125.4, 123.1, 122.9, 120.5, 115.1,
C
3
1
+
Conclusions
110.8, 93.3, 20.9. HRMS (ESI) m/z [M + H ]: calcd for C21
3
H17IN O:
4
1
54.0416, found: 454.0418; IR (KBr): 3434, 2923, 2857, 1749, 1600,
-
1
534, 1481, 1449, 1377, 1231, 1159, 1035, 858, 786, 749, 693 cm .
In conclusion, we successfully developed a facile and general
synthetic rout to obtain etherfied 1, 2, 3-triazole idodides through
O-H arylation / C-H iodation with diacetoxyiodobenzenes. The
convenient process exhibits good functional group tolerance and
provides an efficient access to the 1, 4-disubstituted 1, 2, 3-
triazoles bearing both aryloxy and iodo group.
1-(3-iodo-2-phenoxyphenyl)-4-(2-methoxyphenyl)-1H-1, 2, 3-triazole
o
1
(3d): Yellow solid (98 mg, 70% yield); Mp. 137.5-138.5 C; H NMR (400
MHz, CDCl ) δ = 8.49 (s, 1H), 8.29 (dd, J = 7.7, 1.7 Hz, 1H), 8.00 (dd, J =
3
8.0, 1.2 Hz, 2H), 7.31 – 7.27 (m, 1H), 7.21 (ddd, J = 8.0, 6.2, 3.0 Hz, 3H),
7
.08 – 7.03 (m, 1H), 6.99 (d, J = 7.4 Hz, 1H), 6.94 (d, J = 8.2 Hz, 1H),
13
3
6.77 (d, J = 7.9 Hz, 2H), 3.81 (s, 3H). C NMR (100 MHz, CDCl ) δ =
Experimental Section
156.1, 155.7, 146.0, 143.2, 140.2, 132.0, 129.8, 129.0, 127.8, 127.6,
1
26.2, 124.3, 122.9, 120.9, 118.9, 115.2, 110.8, 93.3, 55.1. HRMS (ESI)
+
3 2
m/z [M + H ]: calcd for C21H17IN O : 470.0365, found: 470.0367; IR (KBr):
3
414, 3193, 2922, 2853, 1645, 1586, 1442, 1393, 1240, 1189, 1154,
General synthetic procedure: 1, 4-Disubstituted 1, 2, 3-triazoles 1 (0.3
-
1
1076, 1021, 861cm .
3
mmol), diacetoxyiodobenzene 2 (3.5 eq., 1.05 mmol), and CH CN (2 mL)
were sequentially added to a 15 mL pressure tube. Then the tube was
o
sealed and stirred at 120 C for 12 h. After consumption of the 1, 4-
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
1
-(3-iodo-2-phenoxyphenyl)-4-(4-methoxyphenyl)-1H-1, 2, 3-triazole
3200, 2924, 2856, 1745, 1667, 1586, 1533, 1474, 1443, 1396, 1304,
o
1
-1
(
3e): Yellow solid (119 mg, 85% yield); Mp. 140.3-141.1 C; H NMR
1228, 1195, 1158, 1021, 970, 915, 864, 750, 689, 642, 489, 440 cm .
(
400 MHz, CDCl ) δ = 8.13 (s, 1H), 8.04 – 7.94 (m, 2H), 7.66 (d, J = 8.7
3
Hz, 2H), 7.20 (td, J = 8.2, 4.1 Hz, 3H), 6.96 (dd, J = 14.8, 8.0 Hz, 3H),
1
3
6
1
1
.74 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H). C NMR (100 MHz, CDCl
3
) δ =
4-(2, 4-dibromophenyl)-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-
o
1
59.7, 155.8, 147.7, 146.2, 140.4, 131.7, 129.8, 127.9, 127.1, 126.1,
triazole (3j): Yellow solid (121 mg, 68% yield); Mp. 124.1-125.6 C; H
+
23.1, 122.7, 120.1, 115.1, 114.2, 93.3, 55.3. HRMS (ESI) m/z [M + H ]:
NMR (500 MHz, CDCl ) δ = 8.73 (s, 1H), 8.24 (s, 1H), 8.01 (dd, J = 18.6,
3
calcd for C21
H
17IN
3
O
2
: 470.0365, found: 470.0367; IR (KBr): 3446, 3130,
7.6 Hz, 2H), 7.45 (d, J = 8.2 Hz, 1H), 7.35 – 7.09 (m, 4H), 6.99 (s, 1H),
13
3
1
064, 2923, 2845, 1738, 1603, 1580, 1485, 1467, 1447, 1292, 1242,
6.75 (d, J = 7.7 Hz, 2H). C NMR (125 MHz, CDCl ) δ = 140.8, 139.9,
3
-
1
182, 1025, 904, 872, 826, 738, 617, 526 cm .
136.9, 134.8, 133.1, 132.3, 129.9, 129.8, 128.0, 127.9, 126.2, 126.1,
+
1
24.6, 123.9, 123.1, 121.6, 115.2, 93.4. HRMS (ESI) m/z [M + H ]: calcd
2 3
for C20H13Br IN O: 597.8450, found: 597.8452; IR (KBr): 3438, 2922,
4
-(2-chlorophenyl)-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-triazole
2856, 1737, 1637, 1586, 1448, 1379, 1332, 1155, 1079, 1031, 874, 788,
o
1
-1
(
3f): Yellow solid (92 mg, 65% yield); Mp. 109.7-110.8 C; H NMR (400
MHz, CDCl ) δ = 8.67 (s, 1H), 8.18 (dd, J = 7.8, 1.6 Hz, 1H), 8.01 (ddd, J
10.7, 8.1, 1.3 Hz, 2H), 7.41 (d, J = 8.0 Hz, 1H), 7.35 (dd, J = 10.8, 4.3
Hz, 1H), 7.28 – 7.16 (m, 5H), 6.97 (t, J = 7.4 Hz, 1H), 6.75 (d, J = 8.1 Hz,
748, 446 cm .
3
=
4-cyclopropyl-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-triazole (3k):
13
o
1
2
1
1
H). C NMR (100 MHz, CDCl
3
) δ = 155.8, 146.1, 144.0, 140.6, 131.6,
Yellow solid (93 mg, 71% yield); Mp. 139.1-140.8 C; H NMR (500 MHz,
31.3, 130.2, 129.8, 129.7, 129.1, 128.7, 127.9, 127.0, 126.2, 124.5,
CDCl ) δ = 8.60 (s, 1H), 8.57 (d, J = 3.5 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H),
3
+
23.04 (s), 115.0, 93.4. HRMS (ESI) m/z [M
14ClIN
+
H ]: calcd for
8.02 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.74 (t, J = 7.7 Hz, 1H),
7.18 (dt, J = 17.7, 7.9 Hz, 4H), 6.93 (t, J = 7.3 Hz, 1H), 6.75 (d, J = 8.2
C
20
H
3
O: 473.9870, found: 473.9872; IR (KBr): 3436, 3201, 2923,
-
1
13
1640, 1589, 1474, 1440, 1393, 1229, 1190, 1112, 1024, 862, 750 cm .
Hz, 2H). C NMR (125 MHz, CDCl ) δ = 155.9, 149.7, 149.4, 146.9,
3
1
40.8, 136.7, 131.6, 129.7, 127.7, 126.4, 123.5, 122.9, 122.8 120.3,
+
115.3, 110.8, 93.2. HRMS (ESI) m/z [M + H ]: calcd for C19
4
H14IN O:
4
-(3-chlorophenyl)-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-triazole
441.0212, found: 441.0214; IR (KBr): 3366, 3177, 3053, 2922, 2854,
o
1
-1
(
3g): Yellow solid (99 mg, 69% yield); Mp. 101.3-102.7 C; H NMR (300
MHz, CDCl ) δ = 8.21 (s, 1H), 7.99 (ddd, J = 19.5, 8.0, 1.3 Hz, 2H), 7.74
s, 1H), 7.60 (dd, J = 6.1, 4.5 Hz, 1H), 7.38 – 7.29 (m, 3H), 7.25 – 7.19
1746, 1588, 1471, 1232, 1020, 863, 757, 496 cm .
3
(
(
13
m, 2H), 7.01 – 6.93 (m, 1H), 6.74 (d, J = 8.0 Hz, 2H). C NMR (75 MHz,
) δ = 155.8, 140.7, 134.8, 131.8, 131.4, 130.1, 129.9, 128.3, 127.9,
27.7, 126.2, 125.8, 123.8, 123.2, 121.3, 115.0, 110.9, 93.3. HRMS (ESI)
4-(3-iodo-2-phenoxyphenyl)-1-(p-tolyl)-1H-1, 2, 3-triazole (3l): Yellow
o
1
CDCl
3
solid (97 mg, 72% yield); Mp. 174.3-175.7 C; H NMR (300 MHz, CDCl )
3
1
δ = 8.49 (dd, J = 7.8, 1.5 Hz, 1H), 8.14 (s, 1H), 7.90 (dd, J = 7.8, 1.5 Hz,
+
m/z [M + H ]: calcd for C20
3
H14ClIN O: 473.9870, found: 473.9872; IR
1H), 7.46 (d, J = 8.4 Hz, 2H), 7.27 (dt, J = 7.3, 3.7 Hz, 4H), 7.16 (t, J =
7.9 Hz, 1H), 7.01 (t, J = 7.4 Hz, 1H), 6.82 (d, J = 7.8 Hz, 2H), 2.40 (s, 3H).
(KBr): 3440, 3165, 3065, 2924, 2855, 1753, 1583, 1476, 1444, 1381,
-
1
13
1230, 1070, 1019, 873, 780, 682, 491cm .
C NMR (100 MHz, CDCl ) δ = 155.9, 150.0, 142.3, 139.8, 138.9, 128.8,
3
1
27.7, 126.3, 122.5, 121.5, 120.4, 115.0, 111.9, 92.6, 21.1. HRMS (ESI)
+
m/z [M + H ]: calcd for C21
3
H17IN O: 454.0416, found: 454.0418; IR (KBr):
4
-(4-chlorophenyl)-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-triazole
3423, 3141, 3041, 2923, 2855, 1728, 1594, 1518, 1483, 1440, 1331,
o
1
-1
(
3h): Yellow solid (103 mg, 72% yield); Mp. 149.1-150.3 C; H NMR (400
MHz, CDCl ) δ = 8.19 (s, 1H), 7.99 (ddd, J = 23.4, 8.0, 1.3 Hz, 2H), 7.67
d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 7.21 (dd, J = 16.0, 7.9 Hz,
1293, 1235, 1160, 1117, 1076, 1041, 874, 815, 779, 717, 688, 524 cm .
3
(
13
3H), 6.97 (t, J = 7.4 Hz, 1H), 6.73 (d, J = 8.1 Hz, 2H). C NMR (100 MHz,
1-(3-iodo-4-phenoxyphenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole (3m):
o
1
CDCl
3
) δ = 155.8, 146.8, 146.2, 140.7, 134.1, 131.5, 129.9, 129.0, 128.6,
Yellow solid (99 mg, 73% yield); Mp. 98.2-99.0 C; H NMR (400 MHz,
+
127.9, 126.9, 126.1, 123.1, 120.9, 115.0, 93.3. HRMS (ESI) m/z [M + H ]:
CDCl ) δ = 8.09 (s, 1H), 7.83 (d, J = 8.1 Hz, 2H), 7.44 – 7.37 (m, 3H),
3
calcd for C20
H
14ClIN
3
O: 473.9870, found: 473.9872; IR (KBr): 3434, 3136,
7.27 (dd, J = 8.8, 4.8 Hz, 4H), 7.06 (dd, J = 8.6, 0.9 Hz, 2H), 6.99 (dd, J =
13
2
1
920, 2854, 1652, 1589, 1478, 1458, 1390, 1240, 1190, 1158, 1090,
8.3, 1.3 Hz, 1H), 2.41 (s, 3H). C NMR (100 MHz, CDCl ) δ = 158.4,
3
-
1
030, 904, 871, 828, 742, 512 cm .
156.1, 147.6, 141.9, 138.3, 130.1, 129.9, 129.6, 127.3, 125.8, 124.4,
+
1
22.6, 121.3, 119.5, 119.0, 89.8, 21.3. HRMS (ESI) m/z [M + H ]: calcd
3
for C21H17IN O: 454.0416, found: 454.0418; IR (KBr): 3421, 2922, 2854,
-
1
4
-(2-bromophenyl)-1-(3-iodo-2-phenoxyphenyl)-1H-1, 2, 3-triazole
1644, 1573, 1474, 1386, 1247, 1198, 1036, 897, 789, 694, 520 cm .
o
1
(
3i): Yellow solid (108 mg, 70% yield); Mp. 99.6-100.8 C; H NMR (500
MHz, CDCl ) δ = 8.71 (s, 1H), 8.03 (d, J = 17.2 Hz, 2H), 7.77 – 7.52 (m,
H), 7.41 (d, J = 35.3 Hz, 2H), 7.22 (dd, J = 20.5, 13.0 Hz, 3H), 6.98 (s,
3
2
1
1
1
2-iodo-4-nitro-1-phenoxybenzene (3n): Yellow solid (65 mg, 63% yield);
13
o
1
H), 6.76 (d, J = 7.1 Hz, 2H). C NMR (125 MHz, CDCl
3
) δ = 155.9,
Mp. 54.6-54.8 C; H NMR (400 MHz, CDCl ) δ = 8.73 (d, J = 2.7 Hz, 1H),
3
40.6, 134.5, 131.8, 130.8, 130.5, 129.8, 129.4, 128.8, 128.5, 127.8,
8.11 (dd, J = 9.1, 2.7 Hz, 1H), 7.44 (tt, J = 4.2, 2.2 Hz, 2H), 7.34 – 7.23
+
13
27.6, 126.2, 124.3, 123.1, 121.2, 115.2, 93.4. HRMS (ESI) m/z [M + H ]:
(m, 1H), 7.15 – 7.04 (m, 2H), 6.74 (d, J = 9.1 Hz, 1H). C NMR (100
3
calcd for C20H14BrIN O: 517.9365, found: 517.9367; IR (KBr): 3441,
MHz, CDCl ) δ = 162.5, 154.6, 142.9, 135.4, 130.3, 125.7, 125.2, 120.3,
3
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
+
1
15.1, 85.9. HRMS (ESI) m/z [M + H ]: calcd for C12
9 3
H IN O: 341.9627,
1-(2-(3-chlorophenoxy)-3-iodophenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole
o
1
found: 341.9629; IR (KBr): 3834, 3759, 3096, 2931, 2851, 2634, 2448,
(3s): Yellow solid (101 mg, 69% yield); Mp. 137.5-138.4 C; H NMR
(400 MHz, CDCl ) δ = 8.14 (s, 1H), 8.02 (dd, J = 8.0, 1.2 Hz, 1H), 7.96 (d,
J = 8.1 Hz, 1H), 7.65 (d, J = 8.0 Hz, 2H), 7.26 – 7.20 (m, 3H), 7.11 (t, J =
2
355, 2068, 1898, 1791, 1694, 1656, 1584, 1488, 1343, 1258, 1181,
3
-
1
1
115, 1026, 896, 813, 750, 684, 497 cm .
8
.2 Hz, 1H), 6.96 (d, J = 8.2 Hz, 1H), 6.79 (t, J = 2.1 Hz, 1H), 6.60 (dd, J
13
=
3
8.3, 2.4 Hz, 1H), 2.38 (s, 3H). C NMR (100 MHz, CDCl ) δ = 145.8,
1
-(3-iodo-2-(o-tolyloxy)phenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole (3o):
140.6, 138.4, 135.3, 130.6, 129.5, 128.3, 127.1, 126.4, 126.4, 125.7,
o
1
Yellow solid (86 mg, 62% yield); Mp. 116.4-117.6 C; H NMR (400 MHz,
CDCl ) δ = 8.07 (s, 1H), 8.03 – 7.94 (m, 2H), 7.61 (d, J = 8.1 Hz, 2H),
.46 (d, J = 8.1 Hz, 1H), 7.21 (d, J = 8.1 Hz, 4H), 6.95 (s, 1H), 6.25 (d, J
123.5, 120.4, 118.9, 115.9, 113.3, 104.9, 89.5, 21.3. HRMS (ESI) m/z [M
+
+ H ]: calcd for C21
3
H16ClIN O: 488.0027, found: 488.0029; IR (KBr): 3392,
3
7
=
1
1
3169, 3060, 2922, 2854, 1745, 1647, 1587, 1471, 1440, 1274, 1232,
13
-1
8.0 Hz, 1H), 2.40 (s, 3H), 2.37 (s, 3H). C NMR (100 MHz, CDCl
3
) δ =
1193, 1079, 1017, 904, 872, 769, 722, 673, 509, 442 cm .
54.0, 140.6, 138.2, 131.4, 129.5, 127.7, 127.3, 127.0, 126.3, 125.6,
25.4, 124.5, 122.8, 120.5, 120.2, 112.2, 110.8, 93.2, 21.3, 21.2. HRMS
+
(ESI) m/z [M + H ]: calcd for C22
3
H19IN O: 468.0573, found: 468.0575; IR
CCDC 1553558 (for 3a), contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
(KBr): 3416, 3142, 2921, 2855, 1749, 1648, 1577, 1479, 1577, 1479,
-
1
1446, 1375, 1228, 1176, 1109, 1031, 872, 815, 753, 515 cm .
1
-(3-iodo-2-(m-tolyloxy)phenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole (3p):
Acknowledgements ((optional))
o
1
Yellow solid (93 mg, 67% yield); Mp. 135.1-136.8 C; H NMR (400 MHz,
CDCl ) δ = 8.17 (s, 1H), 7.99 (ddd, J = 9.4, 8.1, 1.5 Hz, 2H), 7.63 (d, J =
.1 Hz, 2H), 7.45 (s, 1H), 7.23 (s, 2H), 7.21 (s, 2H), 6.95 (s, 1H), 6.77 (d,
3
The authors like to thank the National Natural Science
Foundation of China (Nos. 21262020 and 21662020) for the
financial support.
8
13
J = 7.5 Hz, 1H), 2.37 (s, 3H), 2.35 (s, 3H). C NMR (101 MHz, CDCl
3
) δ
=
1
149.7, 147.8, 139.2, 138.9, 138.2, 129.8, 129.7, 129.3, 127.9, 127.6,
26.61, 125.9, 125.8, 122.7, 120.2, 119.5, 119.4, 117.0, 21.4, 21.3.
Keywords: O-H Arylation • C-H Iodation • 1, 4-Disubstituted 1, 2,
+
HRMS (ESI) m/z [M + H ]: calcd for C22
3
H19IN O: 468.0573, found:
3-Triazoles • Metal-free
4
1
5
68.0575; IR (KBr): 3390, 3178, 2922, 2855, 1750, 1648, 1615, 1576,
451, 1376, 1231, 1137, 1028, 932, 863, 813, 799, 773, 756, 689, 541,
[
1]
a) H. Sharghi, P. Shiri, M. Aberi, Mol Divers. 2014, 18, 559–575; i) G.
Singh, A. Arora, S. S. Mangat, J. Singh, S. Rani, N. Kaur, J. Organomet.
Chem. 2015, 777, 6-15; b) A. Kayet, S. Dey, T. Pathak, Tetrahedron
Lett. 2015, 56, 5521–5524; c) J. Zhou, M. Reidy, C. O’Reilly, D. V.
Jarikote, A. Negi, A. Samali, E. Szegezdi, P. V. Murphy, Org. Lett. 2015,
-
1
15 cm .
1-(2-(2-bromophenoxy)-3-iodophenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole
17, 1672−1675; d) D. Gangaprasad, J. P. Raj, T. Kiranmye, S. S. Sadik,
o
1
(
3q): Yellow solid (111 mg, 70% yield); Mp. 165.8-166.4 C; H NMR
J. Elangovan, RSC Adv. 2015, 5, 63473–63477; e) J. R. Johansson, T.
Beke-Somfai, A. S. Stalsmeden, N. Kann, Chem. Rev. 2016, 116,
14726−14768; f) K. Yamamoto, T. Bruun, J. Y. Kim, L. Zhang, M.
Lautens, Org. Lett. 2016, 18, 2644−2647; g) R. W. Kubiak, J. D.
Mighion, S. M. Wilkerson-Hill, J. S. Alford, T. Yoshidomi, H. M. L.
Davies; Org. Lett. 2016, 18, 3118−3121; h) W. Wang, F. Wei, Y. Ma, C.
H. Tung, Z. Xu, Org. Lett. 2016, 18, 4158−4161; i) K. Lal, P. Yadav, A.
Kumar, Med Chem Res. 2016, 25, 644–652; j) M. Bhardwaj, B. Jamwal,
S. Paul, Catal Lett. 2016, 146, 629–644; k) P. Dhamodharan, K. Sathya,
M. Dhandapani, Physica B. 2017, 508, 33–40; l) T. A. Hilimire, J. M.
Chamberlain, V. Anokhina, R. P. Bennett, O. Swart, J. R. Myers, J. M.
Ashton, R. A. Stewart, A. L. Featherston, K. Gates, E. D. Helms, H. C.
Smith, S. Dewhurst, B. L. Miller, ACS Chem. Biol. 2017, 12, 1674−1682;
m) D. Gangaprasad, J. P. Raj, T. Kiranmye, R. Sasikala, K. Karthikeyan,
S. Kutti Rani, J. Elangovan, Tetrahedron Lett. 2016, 57, 3105–3108; n)
J. Thomas, V. Goyvaerts, S. Liekens, W. Dehaen, Chem. Eur. J. 2016,
(
300 MHz, CDCl ) δ = 8.44 (s, 1H), 8.03 (dd, J = 7.9, 2.6 Hz, 2H), 7.71 (d,
3
J = 8.0 Hz, 2H), 7.56 – 7.45 (m, 1H), 7.25 (d, J = 3.8 Hz, 3H), 7.02 (t, J =
7
1
.8 Hz, 1H), 6.82 (t, J = 7.1 Hz, 1H), 6.31 (d, J = 7.4 Hz, 1H), 2.38 (s, 3H).
3
3
C NMR (75 MHz, CDCl ) δ = 151.7, 149.0, 143.2, 140.2, 133.8, 129.5,
1
9
5
1
28.6, 128.3, 127.1, 126.0, 125.7, 124.2, 120.5, 119.5, 113.6, 110.8,
+
9.6, 92.9, 21.3. HRMS (ESI) m/z [M + H ]: calcd for C21
3
H16BrIN O:
31.9521, found: 531.9523; IR (KBr): 3387, 3164, 3079, 2920, 2854,
-
1
764, 1648, 1578, 1459, 1236, 1020, 873, 742, 658, 511 cm .
1
-(2-(2-chlorophenoxy)-3-iodophenyl)-4-(p-tolyl)-1H-1, 2, 3-triazole
o
1
(
3r): Yellow solid (106 mg, 73% yield); Mp. 152.2-153.5 C; H NMR (400
MHz, CDCl ) δ = 8.41 (s, 1H), 8.02 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 8.1
Hz, 2H), 7.34 (dd, J = 7.9, 1.6 Hz, 1H), 7.27 – 7.20 (m, 3H), 6.93 (dtd, J =
3
22, 9966–9970.
13
3
6.7, 7.6, 1.5 Hz, 2H), 6.34 (dd, J = 8.2, 1.3 Hz, 1H), 2.38 (s, 3H).
C
[2]
a) Y. Gao, Y. Lam, Org. Lett. 2006, 8, 3283-3285; b) F. Alonso, Y.
Moglie, G. Radivoy, M. Yus, J. Org. Chem. 2013, 78, 5031−5037; c) A.
Lauria, R. Delisi, F. Mingoia, A. Terenzi, A. Martorana, G. Barone, A. M.
Almerico, Eur. J. Org. Chem. 2014, 3289–3306; d) M. Nasr-Esfahani, I.
Mohammadpoor-Baltork, A. R. Khosropour, M. Moghadam, V. Mirkhani,
S. Tangestaninejad, H. A. Rudbari, J. Org. Chem. 2014, 79, 1437−1443;
e) K. B. Mishra, V. K. Tiwari, J. Org. Chem. 2014, 79, 5752−5762; f) D.
Dontsova, S. Pronkin, M. Wehle, Z. Chen, C. Fettkenhauer, G. Clavel,
M. Antonietti, Chem. Mater. 2015, 27, 5170−5179; g) S. Ahamad, R.
Kant, K. Mohanan, Org. Lett. 2016, 18, 280−283; h) S. Shin, J. Y Son,
3
NMR (101 MHz, CDCl ) δ = 150.8, 148.1, 145.3, 140.3, 138.2, 131.1,
1
1
4
1
30.8, 129.5, 128.3, 127.9, 127.2, 126.1, 125.7, 123.8, 121.9, 120.4,
+
13.9, 92.9, 21.3. HRMS (ESI) m/z [M + H ]: calcd for C21
3
H16ClIN O:
88.0027, found: 488.0029; IR (KBr): 3430, 3149, 2922, 1643, 1583,
-
1
475, 1390, 1241, 1029, 876, 816, 748, 512 cm .
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
C. Choi, S. Kim, P. H. Lee, J. Org. Chem. 2016, 81, 11706−11715; i) A.
Goitia, E. Gomez-Bengoa, A. Correa, Org. Lett. 2017, 19, 962−965; j)
V. O. Filimonov, L. N. Dianova, K. A. Galata, T. V. Beryozkina, M. S.
Novikov, V. S. Berseneva, O. S. Eltsov, A. T. Lebedev, P. A. Slepukhin,
V. A. Bakulev, J. Org. Chem. 2017, 82, 4056−4071.
c) N. K. Sebbar, M. E. M. Mekhzoum, E. M. Essassi, Z. Abdelfettah, Y.
Ouzidan, Y. K. Rodi, A. Talbaoui, Y. Bakri, J.Mar.Chim.Heterocycl.
2016, 15, 1-11; d) Refinel, A. Alif, M. Khairat, Deswati, Der Pharma
Chemica, 2016, 8, 236-242.
[11]
[12]
a) R. Huisgen, Angew. Chem., Int. Ed. Engl. 1963, 2, 633-638; b) R.
Huisgen, R. Knorr, L. ꢀꢁꢂiꢃꢄ, G. Szeimies, Chem. Ber. 1965, 98, 4014-
4018.
[
3]
a) A. Massarotti, A. Brunco, G. Sorba, G. C. Tron, J. Chem. Inf. Model.
014, 54, 396−406; b) T. Miura, Y. Funakoshi, M. Murakami, J. Am.
2
Chem. Soc. 2014, 136, 2272−2275; c) Y. C. Wang, Y. Y. Xie, H. E. Qu,
H. S. Wang, Y. M. Pan, F. P. Huang, J. Org. Chem. 2014, 79,
a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew.
Chem., Int. Ed. 2002, 41, 2596-2601; b) L. V. Lee, M. L. Mitchell, S. J.
Huang, V. V. Fokin, K. B. Sharpless, C. H. Wong, J. Am. Chem. Soc.
2003, 125, 9588-9593.
4463−4469; d) A. Bhaumik, S. Samanta, T. Pathak, J. Org. Chem. 2014,
79, 6895−6904; e) J. Guo, B. Yu, Y. N. Wang, D. Duan, L. L. Ren, Z.
Gao, J. Gou, Org. Lett. 2014, 16, 5088−5091; f) Y. Chen, G. Nie, Q
Zhang, S. Ma, H. Li, Q. Hu, Org. Lett. 2015, 17, 1118−1121; g) A.
Irastorza, J. M. Aizpurua, A. Correa, Org. Lett. 2016, 18, 1080−1083; h)
L.L. Zhu, X. Q. Xu, J. W. Shi, B. L. Chen, Z. Chen, J. Org. Chem. 2016,
[13]
a) C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67,
3057-3062.
[14] a) M. Belkheira, D. Abed, J. M. Pons, C. Bressy, Chem. Eur. J. 2011,
17, 12917-12921; b) L. Wang, S. Peng, L. J. T. Danence, Y. Gao, J.
Wang, Chem. Eur. J. 2012, 18, 6088-6093; c) D. B. Ramachary, A. B.
Shashank, Chem. Eur. J. 2013, 19, 13175-13181; d) S. S. V.
Ramasastry, Angew. Chem. Int. Ed. 2014, 53, 14310-14312; e) W. Li, Z.
Du, J. Huang, Q. Jia, K. Zhang, J. Wang, Green Chem. 2014, 16,
3003–3006; f) J. Thomas, S. Jana, S. Liekensb, W. Dehaen, Chem.
Commun, 2016, 52, 9236-9239;
8
1, 3568−3575; i) Z. Zhang, S. Yang, J. Li, X. Liao, J. Org. Chem. 2016,
1, 9639−9646.
8
[
4]
a) A. Boyer, Org. Lett. 2014, 16, 5878−5881; b) S. Koguchi, K. Izawa,
ACS Comb. Sci. 2014, 16, 381−385; c) P. Kumar, C. Joshi, A. K.
Srivastava, P. Gupta, R. Boukherroub, S. L. Jain, ACS Sustainable
Chem. Eng. 2016, 4, 69−75; d) D. Gangaprasad, J. P. Raj, T. Kiranmye,
S. S. Sadik, J. Elangovan, RSC Adv. 2015, 5, 63473–63477; e) M. Teci,
M. Tilley, M. A. McGuire, M. G. Organ, Org. Process Res. Dev. 2016,
[15] a) W. Li, Z. Du, K. Zhang, J. Wang, Green Chem. 2015, 17, 781–784; b)
W. Li, J. Wang, Angew. Chem. Int. Ed. 2014, 53, 14186-14190; c) Y.
Chen, G. Nie, Q. Zhang, S. Ma, H. Li, Q. Hu, Org. Lett. 2015, 17, 1118-
1121; d) S. Rohilla, S. S. Patel, N. Jain, Eur. J. Org. Chem. 2016, 847-
854; e) D. Janreddy, V. Kavala, C. W. Kuo, W. C. Chen, C. Ramesh, T.
Kotipalli, T. S. Kuo, M. L. Chen, C. H. He, C. F. Yao, Adv. Synth. Catal.
2013, 355, 2918 – 2927; f) J. P. Wan, S. Cao, Y. Liu, Org. Lett. 2016,
18, 6034−6037; g) J. P. Wan, S. Cao, Y. Liu, J. Org. Chem. 2015, 80,
9028−9033.
2
0, 1967−1973; f) N. V. Rostovskii, J. O. Ruvinskaya, M. S. Novikov, A.
F. Khlebnikov, L. A. Smetanin, A. V. Agafonova, J. Org. Chem. 2017,
2, 256−268.
8
[
5] a) D. Amantini, F. Fringuelli, O. Piermatti, F. Pizzo, E. Zunino, L. Vaccaro,
J. Org. Chem. 2005, 70, 6526-6529; b) M. J. Giffin, H. Heaslet, A. Brik,
Y. C. Lin, G. Cauvi, C. H. Wong, D. E. McRee, J. H. Elder, C. D. Stout,
B. E. Torbett, J. Med. Chem. 2008, 51, 6263–6270; c) N. Pribut, C. G. L.
Veale, A. E. Basson, W. A. L. Otterlo, S. C. Pelly, Bioorg. Med. Chem.
Lett. 2016, 26, 3700–3704; d) S. Jana, S. Iram, J. Thomas, M. Q. Hayat,
C. Pannecouque, W. Dehaen, Molecules. 2017, 22, 303-316.
[16] a) X. Wang, K. Sidhu, L. Zhang, S. Campbell, N. Haddad, D. Reeves, D.
Krishnamurthy, C. H. Senanayake, Org. Lett. 2009, 11, 5490-5493; b) X.
Wang, L. Zhang, D. Krishnamurthy, C. H. Senanayake, P. Wipf, Org.
Lett. 2010, 12, 4632-4635; c) S. Xu, X. Zhuang, X. Pan, Z. Zhang, L.
Duan, Y. Liu, L. Zhang, X. Ren, K. Ding, J. Med. Chem. 2013, 56,
4631−4640; d) K. Wang, M. Chen, Q. Wang, X. Shi, J. K. Lee, J. Org.
Chem. 2013, 78, 7249-7258; e) A. Boyer, Org. Lett. 2014, 16, 1660-
1663; f) C. E. Kim, S. Park, D. Eom, B. Seo, P. H. Lee, Org. Lett. 2014,
16, 1900-1903; g) X. Lei, L. Li, Y. P. He, Y. Tang, Org. Lett. 2015, 17,
5224-5227; h) Z. Monasterio, A. Irastorza, J. I. Miranda, J. M. Aizpurua,
Org. Lett. 2016, 18, 2511-2514; i) Y. Li, Q. Zhang, Q. Du, H. Zhai, Org.
Lett. 2016, 18, 4076-4079; j) X. Lei, M. Gao, Y. Tang, Org. Lett. 2016,
18, 4990−4993; k) K. Huang, G. Sheng, P. Lu, Y. Wang, J. Org. Chem.
2017, 82, 5294−5300; l) X. Deng, X. Lei, G. Nie, L. Jia, Y. Li, Y. Chen, J.
Org. Chem. 2017, 82, 6163−6171; j) J. P. Wan, D. Hu, Y. Liu, S. Sheng,
ChemCatChem. 2015, 7, 901-903.
[
6]
a) D. M. Mazur, M.E. Zimens, V. A. Bakulev, A. T. Lebedev, J. Pharm.
Biomed. Anal. 2017, 145, 315–321; b) B. Kummari, N. Polkam, P.
Ramesh, H. Anantaraju, P. Yogeeswari, J. S. Anireddy, S. D.
Guggilapud, B. N. Babu, RSC Adv. 2017, 7, 23680–23686.
[
7]
a) A. B. Lopes, P. Wagner, R. O. M. A. Souza, N. L. Germain, J. Uziel,
J. J. Bourguignon, M. Schmitt, L. S. M. Miranda, J. Org. Chem. 2016,
81, 4540−4549; b) A. Gigante, A. G. S. Juan, L. Delang, C. Li, O.
Bueno, A. M. Gamo, E. M. Priego, M. J. Camarasa, D. Jochmans, P.
Leyssen, E. Decroly, B. Coutard, G. Querat, J. Neyts, M. J. Perez,
Antiviral Research. 2017, 144, 216-222; c) D. M. Mazur, M. E. Zimens,
V. A. Bakulev, A. T. Lebedev, J. Pharm. Biomed. Anal. 2017, 145, 315–
3
21.
8] a) W. Tan, Q. Li, F. Dong, S. Qiu, J. Zhang, Z. Guo, Carbohydr. Polym.
017, 160, 163–171; b) N. Fu, S. Wang, Y. Zhang, C. Zhang, D. Yang,
[
[
[
2
L. Weng, B. Zhao, L. Wang, Eur. J. Med. Chem. 2017, 136, 596-602; c)
T. F. Santos, J. B. Jesus, P. M. Neufeld, A. K. Jordão, V. R. Campos, A.
C. Cunha, H. C. Castro, M. C. B. V. Souza, V. F. Ferreira, C. R.
Rodrigues, P. A. Abreu, Med Chem Res. 2017, 26, 680–689; d) B.
Neelamma, J. U. Rani, S. Vianala, M. K. Thupurani, Der Pharma
Chemica. 2016, 8, 124-131.
[17] a) Q. Tian, X. Chen, W. Liu, Z. Wang, S. Shia, C. Kuang, Org. Biomol.
Chem. 2013, 11, 7830-7833; b) S. Shi, W. Liu, P. Hea, C. Kuang,Org.
Biomol. Chem. 2014, 12, 3576–3580; c) X. Yu, Z. D. Huang, W. Liu, S.
P. Shi, C. X. Kuang, Org. Biomol. Chem. 2015, 13, 4459-4465; d) P. He,
Q. Tiana, C. Kuang, Org. Biomol. Chem. 2015, 13, 7146–7148; e) S.
Shi, C. Kuang, J. Org. Chem. 2014, 79, 6105−6112; f) W. Liu, Y. Li, B.
Xu, C. Kuang, Org. Lett. 2013, 15, 2342-2345; g) Z. Wang, C. Kuang,
Adv. Synth. Catal. 2014, 356, 1549-1554; h) W. Shi, Z. Shi, Chin. J.
Chem. 2014, 32, 974—980. i) R. Jeyachandran, H. K. Potukuchi, L.
Ackermann, Beilstein J. Org. Chem. 2012, 8, 1771–1777; j) Z. Shen, G.
Cera, T. Haven, L. Ackermann, Org. Lett. 2017, 19, 3795-3798; k) L.
Ackermann, H. K. Potukuchi, Org. Biomol. Chem. 2010, 8, 4503–4513;
l) X. Tian, F. Yang, D. Rasina, M. Bauer, S. Warratz, F. Ferlin, L.
Vaccaro, L. Ackermann, Chem. Commun. 2016, 52, 9777-9780; m) L.
Ackermann, H. K. Potukuchi, D. Landsberg, R. Vicente, Org. Lett. 2008,
10, 3081-3084; n) L. Ackermann, R. Jeyachandran, H. K. Potukuchi, P.
Novak, L. Buttner, Org. Lett. 2010, 12, 2056-2059.
9]
a) T. A. Bakka, M. B. Strøm, J. H. Andersen, O. R. Gautun, Bioorg. Med.
Chem. Lett. 2017, 27, 1119-1123; b) R. P. Jadhav, H. N. Raundal, A. A.
Patil, V. D. Bobade, J. Saud. Chem. Soc. 2017, 21, 152–159; c) M.
Bhata, G. K. Nagaraja, R. Kayarmara, R. P. K. Sreedhara, S. Biswasc,
S. R. Mohammed , Der Pharma Chemica. 2016, 8, 200-221; d) B. F.
Abdel-Wahab, R. E. Khidre, H. A. lMohamed, G. A. El-Hiti, Arab J Sci
Eng. 2017, 42, 2441–2448; e) D. S. Reddy, N. Seelam, S. M. Reddy,
Asian J. Chem. 2017, 29, 631-634.
10] a) T. G. Kraljevic, A. Harej, M. Sedic, S. K. Pavelic, V. Stepanic, D.
Drenjancevic, J. Talapko, S. Raic-Malic, Eur. J. Med. Chem. 2016, 124,
794-808; b) P. Khaligh, P. Salehi, M. Bararjanian, A. Aliahmadi, H. R.
Khavasi, S. Nejad-Ebrahimi, Chem. Pharm. Bull. 2016, 64, 1589–1596;
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
[
18]
a) F. Zhao, Z. Chen, Y. Liu, K. Xie, Y. Jiang, Eur. J. Org. Chem. 2016,
Y. Jiang, Synlett. 2017, 28, 1496-1500; e) Y. Jiang, X. Ma, F. Zhao, C.
Han, Synlett. 2017, 28, 713-718.
5
971–5979; b) F. Zhao, Y. Liu, S. Yang, K. Xie, Y. Jiang, Org. Chem.
Front. 2017, 4, 1112–1115; c) F. Zhao, Z. Chen, X. Ma, S. Huang, Y.
Jiang, Tetrahedron Lett. 2017, 58, 614–617; d) Y. Liu, W. Zhang, K. Xie,
[19]
Y. Liu, F. Zhao, H. Zhou, K. Xie, Y. Jiang, J. Chem. Sci. 2017, 129,
289–294.
[
20] W. Hao, Y. Liu, Beilstein J. Org. Chem. 2015, 11, 2132–2144.
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.201701114
FULL PAPER
FULL PAPER
Key Topic* O-H Arylation • C-H
Iodation • 1, 4-Disubstituted 1, 2, 3-
triazoles • Metal-free
Yaowen Liu, Jianhua Yang, Xinyuan Ma,
Chunmei Han, and Yubo Jiang *
Page 1. – Page 6.
Metal-free synthesis of etherfied 1, 2,
A method for the synthesis of etherfied 1, 2, 3-triazole idodides from 1, 4-
disubstituted 1, 2, 3-triazoles under metal free conditions has been developed. In
3-triazole idodides through O-H
the presence of ArI(OAc)
2
, a range of 1, 2, 3-triazole substrates bearing hydroxyl
arylation / C-H iodation with
diacetoxyiodobenzenes
group undergo the direct O-H arylation and C-H iodation simultaneously and was
modified in good to excellent yields.
*
Functionalized triazoles
This article is protected by copyright. All rights reserved.