Full text of DOI:10.1080/00397911.2018.1514050

Synthetic Communications
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1,2,3-Triazole N(2)-chelated C–S coupling: Access to
ortho methylthiolated 1,2,3-triazoles
Shengtao Yu, Yaowen Liu, Jiazhuang Wang, Fang Luo, Huiling Cheng & Yubo
Jiang
To cite this article: Shengtao Yu, Yaowen Liu, Jiazhuang Wang, Fang Luo, Huiling Cheng & Yubo
Jiang (2018): 1,2,3-Triazole N(2)-chelated C–S coupling: Access to ortho methylthiolated 1,2,3-
triazoles, Synthetic Communications, DOI: 10.1080/00397911.2018.1514050
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https://doi.org/10.1080/00397911.2018.1514050
1
,2,3-Triazole N(2)-chelated C–S coupling: Access to ortho
methylthiolated 1,2,3-triazoles
Shengtao Yu, Yaowen Liu, Jiazhuang Wang, Fang Luo, Huiling Cheng, and
Yubo Jiang
Faculty of Science, Kunming University of Science and Technology, Kunming, China
ABSTRACT
ARTICLE HISTORY
CuF -mediated selective C-S coupling of 1,4-disubstituted 1,2,3-tri-
Received 28 April 2018
2
azole halides using the widely available DMSO as the methylthiola-
tion reagent were achieved through the chelation of N(2) atom in
triazole ring. The ortho- C-halogen bond in N(1) aryl was selectively
coupled, while other C-halogen bonds remained, generating 1,4-
disubstituted 1,2,3-triazoles bearing aryl methyl thioether fragment.
KEYWORDS
CuF2-mediated; DMSO;
methylthiolation;
1
,2,3-triazoles
GRAPHICAL ABSTRACT
Introduction
Aryl methyl thioethers are commonly found in many pharmaceuticals and agrochemi-
cals, especially in the field of some biology inhibitors such as monoamine oxidase A
[
1–6]
(
MAO-A), cyclooxygenase-2 (COX-2), cytokine release, and etc (Figure 1).
In add-
[
7–9]
[10–16]
ition, they also act as important structural moieties
and vital intermediates,
which can be transformed into corresponding sulfoxides, thiols, and used for
cross-couplings.
Consequently, broad efforts have been devoted in exploring efficient and facile
[
17–21]
accesses for the synthesis of aryl methyl thioethers.
Mostly, the classical accesses
to aryl methyl sulfides usually depend on the combination of aryl lithiums with
[
22]
dimethyl disulfides
or nucleophilic aromatic substitution of aryl halides with thiolate
[
23]
anions, including sodium methylthiolate (NaSMe)
or (methylthio)trimethylsilanes
Inspiringly, the widely available dimethyl sulfoxide (DMSO) was found
as an applicable methylthiolation reagent, which was highly valued then. In the early
[24]
(TMSSMe).
[
25]
year of 2010, Qing group
explored CuF -mediated selective methylthiolation of aryl
2
CONTACT Huiling Cheng
ynchenghl@163.com, Yubo Jiang
ybjiang@kmust.edu.cn
Faculty of Science,
Kunming University of Science and Technology, Kunming 650500, China.
Supplemental data for this article can be accessed on the the publisher’s website.
ß 2018 Taylor & Francis Group, LLC

2
S. YU ET AL.
Figure 1. Examples of biology inhibitors.
C–H bonds with DMSO under the direction of 2-pyridyl. Thereafter, methylthiolation
[
26]
of aryl halides with DMSO was also reported by Cheng,
which was mediated by
[
27]
CuBr or CuI with excellent tolerance of functional group. Recently, Huang
reached
copper-catalyzed ortho-thiomethylation of benzamides through 8-aminoquinoline-
assisted C–H activation with dimethyl sulfoxide. Simultaneously, Tan group realized
[
28]
decarboxylative methylthiolation of aromatic carboxylate salts with DMSO.
Meanwhile, from the breakthrough of Sharpless’s highly efficient Cu-catalyzed cyclo-
addition reaction of terminal alkyne with azide, a large number of 1,2,3-triazoles have
[
29–32]
been constructed,
which were widely applied in many fields such as organic syn-
[
33–39]
thesis, materials, and biochemistry.
However, most methods still suffer from the
synthesis of target with complicated structure as the corresponding functionalized
alkyne and azide needed are unobtainable. As an alternative, the strategy of direct modi-
fication of 1,2,3-triazoles emerges as a powerful access for the construction of function-
alized 1,2,3-triazoles. Kuang, Wu, Liu, Correa, Ackmann, and our groups respectively
explored the modifications of 1,2,3-triazoles, mainly including C–C, C–N, and C–O
couplings, generating functionalized molecules bearing biphenyl, nitryl, and ether frag-
ment, which enormously enriched the kinds of 1,2,3-triazoles for various
[
40–45]
applications.
In the above reports the regioselective couplings occurred only on C(4) aryl of the
,4-disubstituted 1,2,3-triazoles as the N(3) atom was selectively chelated in the catalytic
1
cycle. To my knowledge, the types were mainly limited in C–C, C–N, and C–O cou-
pling, while the C–S bond formation has not been reported and there was scarcely no
work focused on the N(1) aryl till now. Herein, we would like to demonstrate a process
of C–S formation on the N(1) aryl, in which N(2) atom should be chelated in the in
the active mediate revolved.
Results and discussion
In our initial study, 1-(2-chlorophenyl)-4-(p-tolyl)-1H-1,2,3-triazole (1a) was chosen as
model substrate for optimization of the reaction conditions. We investigated the effects
of catalyst, oxide, and temperature respectively, as summarized in Table 1. No product
of 1-(2-(methylthio)phenyl)-4-(p-tolyl)-1H-1,2,3-triazole 2a was obtained when the reac-
tion was catalyzed by Pd(OAc) (0.2 equiv.), using K S O (2 equiv.) as the oxide, and
2
2 2 8
ꢀ
DMSO as the thiomethylation reagent and solvent under 150 C (Table 1, entry 1). The
product was obtained if 0.2 equivalent of CuF was applied to mediate the reaction,
2
though the yield was low (Table 1, entry 2). When the amount of CuF was increased
2

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3
a
Table 1. Optimization of reaction conditions .
b
Entry
Additive (Equiv.)
Pd(OAc) (0.2)
Oxide (Equiv.)
Temp.
2a (%)
ꢀ
1
2
3
4
5
6
7
8
9
2
K
K
K
K
K
2
S
2
S
2
S
2
S
2
S
2
O
2
O
2
O
2
O
2
O
8
8
8
8
8
(2)
(2)
(2)
(2)
(2)
150 C
0
9
19
0
20
46
53
88
0
26
25
0
ꢀ
CuF
CuF
CuF
CuF
CuF
CuF
CuF
CuF
CuF
2
2
2
2
2
2
2
2
2
(0.2)
(4)
(4)
(4)
(4)
(4)
(4)
(4)
(4)
150 C
ꢀ
150 C
ꢀ
140 C
ꢀ
160 C
ꢀ
(NH
Ag CO
TBHP (2)
4
)
2
S
3
2
O
(2)
8
(2)
150 C
ꢀ
2
150 C
ꢀ
150 C
ꢀ
O
2
150 C
ꢀ
1
1
1
1
1
1
1
a
0
1
2
3
4
5
6
Cu(OAc)
2
(2)
150 C
ꢀ
Cu(OTf)
2
(4)
TBHP (2)
TBHP (2)
TBHP (2)
TBHP (2)
TBHP (2)
TBHP (2)
150 C
ꢀ
CuBr
CuCl
2
(4)
(4)
100 C
ꢀ
2
90 C
0
ꢀ
CuO (4)
110 C
36
66
83
ꢀ
CuF
CuF
2
(3)
(5)
100 C
ꢀ
2
100 C
The reaction conditions are as follows: 1,2,3-triazole chloride 1a (0.3 mmol), additive, oxide (0.6 mmol), and
DMSO (2 mL).
Isolated yield.
b
to 4 equivalents, a better yield of 19% could be obtained (Table 1, entry 3). The reaction
temperature has a distinct influence on this conversion as no product was detected
ꢀ
when the temperature was decreased to 140 C (Table 1, entry 4). Higher temperature
seemed of no obvious use, as the yield was not increased when the reaction was con-
ꢀ
ducted under 160 C (Table 1, entry 5).
We then explored the influence of oxides and found that TBHP was the best choice,
under which a satisfying yield of 88% could be obtained and others like (NH ) S O ,
4
2 2 8
Ag CO , Cu(OAc) , and O were comparatively inferior (Table 1, entries 6-10). Other
2
3
2
2
cuprous salts such as Cu(OTf) , CuBr , CuCl , and CuO are not so efficient than CuF
2
2
2
2
to this reaction (Table 1, entries 11–14). The amount of CuF screenings showed that 4
2
equivalent was superior as the yield decreased to 66% when we adjusted CuF to 3
2
equivalent and more CuF adding played no obvious positive role in the reaction (Table
2
1
, entries 15–16). So, the best conditions for this transformation is CuF (4 eq.), TBHP
2
ꢀ
(2 eq.), and DMSO under 150 C for 24 h (Table 1, entry 8).
With the optimized conditions in hand, the selective C–S coupling reactions were
carried out with a range of 1, 4-disubstituted 1,2,3-triazole chloride 1 in DMSO, gener-
ating methylthiolation products with good to excellent yields. As shown in Table 2, the
coupling reactions of 1,2,3-triazole substrates containing electron-donating group (such
as –CH , –OH, –OCH ) or electron-withdrawing group (such as –F, –Cl) on its C(4)-
3
3
aryl could all go smoothly (Table 2, 2a–2h). It was observed that electron-donating sub-
stituents are beneficial to this C–S coupling, leading to higher yields, and some elec-
tron-withdrawing groups seemed unfavorable to this reaction (Table 2, 2a–2c vs 2f–2h).
Moreover, hydroxyl active group was tolerated in the system and a good yield was

4
S. YU ET AL.
a,b
Table 2. N(2)-coordinated C-S coupling of 1,4-disubstituted 1,2,3-triazole chlorides
.
a
Reaction conditions: 1,4-disubstituted 1,2,3-triazole chloride 1 (0.3 mmol), CuF
2
(1.2 mmol), TBHP (0.6 mmol), and DMSO
ꢀ
(
2 mL) were mixed and stirred at 150 C for 24h.
b
Isolated yield.
generated (Table 2, 2d). It is worth to be noted that substituent of -Cl on meta- or
para- position of C(4)-aryl in the substrates was found to be perfectly compatible, which
was probably owing to the effect of N(2) coordination of the 1,2,3-triazole ring (Table
2, 2g-2h). Except 1,4-diaryl 1,2,3-triazoles, molecules with 4-thienyl, 4-pentyl, 4-cyclo-
propyl, and 1-benzyl group can serve as the substrates, and good to excellent yields
were obtained (Table 2, 2i–2l).
We then explored the coupling reactions of other C–X bonds (X ¼ I, Br, and F) by
using 1-(2-halophenyl)-4-(p-tolyl)-1H-1,2,3-triazole (Scheme 1, 1m–1o) as the substrates.
Obviously as shown in Scheme 1, good and excellent yields were obtained from the tri-
azole iodide and bromide respectively (1m, 1n). While no methylthiolation molecule
was observed when the triazole fluoride was chosen for the coupling, which may be due
to the high stability of C–F bond (1o).
To evaluate the N(2) coordination role of the 1,2,3-triazole ring furtherly, we carried
out the reaction of 1-(3-chlorophenyl)-4-(p-tolyl)-1H-1,2,3-triazole 1p and 1-(2-chloro-
phenyl)-1H-pyrrole 1p, in which no directing effect could occur on the C–Cl bond
(Scheme 2). After the reaction was conducted under standard conditions, no target mol-
ecules were detected, which explained that the N(2) coordination of the 1,2,3-triazole
ring should play an important role in this methylthiolation process.

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5
Scheme 1. Reactions of other triazole halides.
Scheme 2. Experiments of testing the N(2) coordination role.
Scheme 3. Gram scale experiment.
To test the scalability of the current method, the gram scale reaction of 1-(2-chloro-
phenyl)-4-(p-tolyl)-1H-1,2,3-triazole 1a (4.0 mmol, 1.079 g) as the starting materials was
carried out under the standard conditions, and the product 2a was isolated in 91% yield
(Scheme 3).
Conclusion
In conclusion, we have demonstrated the CuF-mediated regioselective C–S coupling of
1, 4-disubstituted 1,2,3-triazole halides, using DMSO as a methylthiolation source, in
which the ortho- C–X (X ¼ Cl, Br, I) bond in N(1) aryl can be selectively aryloxylated
while other C–X bonds remained, owing to the coordination of the N(2) atom in the

6
S. YU ET AL.
1
,2,3-triazole ring. The obtained products contain two important structures of 1,2,3-tri-
azole and aryl methyl thioether, which may serve as meaningful molecules in the future.
Experimental
1
13
H and C NMR spectra were recorded with a Bruker ACF400 spectrometer
(
400 MHz) in CDCl with TMS as an internal standard. All reactions were monitored
3
by TLC analysis with HuanghaiGF 254 silica gel-coated plates. Column chromatography
was conducted using 300 to 400 mesh silica gel at medium pressure. Infrared spectra
were recorded on the Bruker Vertex Series FTIR (KBr) and were reported in reciprocal
ꢁ1
centimeters (cm ). Melting points were obtained using the B u€ chi melting point appar-
atus and were uncorrected. HRMS spectra were recorded on the Waters Micromass
Premier Q-TOF spectrometer.
General procedures
1
, 4-Disubstited 1,2,3-triazole halide 1 (0.3 mmol), CuF (1.2 mmol), t-butylhydroperox-
2
ide (TBHP) (0.6 mmol), and DMSO (2 mL) were added to a 15 mL pressure tube. Then
ꢀ
the tube was sealed with a teflon screwcap and stirred at 150 C for 24 h. After con-
sumption of 1, 4-Disubstited 1,2,3-triazole halide 1 monitored by TLC analysis, the mix-
ture was added with H O (15 mL) and extracted with EtOAc (3 ꢂ 15 mL). The
2
combined organic layer was washed with brine (3 ꢂ 5 mL), dried over Na SO and con-
2
4
centrated under reduced pressure to afford a crude product. Purification by column
chromatography on silica gel afforded the desired product 2.
Spectral data for the selected compounds
Compound 2a:
ꢀ
1
Yellow solid; mp 90–92 C; H NMR (600 MHz, CDCl ) d 8.10 (s, 1H), 7.81 (d,
3
J ¼ 8.0 Hz, 2H), 7.51–7.47 (m, 2H), 7.43 (d, J ¼ 8.1 Hz, 1H), 7.33 (t, J ¼ 7.6 Hz, 1H), 7.27
1
3
(
1
2
d, J ¼ 7.7 Hz, 2H), 2.40 (s, 3H), 2.39 (s, 3H); C NMR (150 MHz, CDCl ) d 147.59,
3
38.13, 135.49, 135.07, 130.18, 129.53, 127.50, 127.47, 126.72, 125.91, 125.76, 121.22,
1.30, 15.93; IR (KBr): 3404,2919, 1474, 1229, 1032, 815,749 cm ; HRMS Calcd for
ꢁ
1
þ
[
C H N S] : 282.1059, Found: 282.1057.
1
6
16 3
Compound 2c:
Light yellow solid; mp 125–128 C; H NMR (400 MHz, CDCl ) d 8.06 (s, 1H), 7.87 –
ꢀ
1
3
7
7
1
5
7
.83 (m, 2H), 7.51–7.45 (m, 2H), 7.42 (dd, J ¼ 8.3, 1.3 Hz, 1H), 7.35–7.29 (m, 1H),
13
.01–6.97 (m, 2H), 3.85 (s, 3H), 2.38 (s, 3H); C NMR (100 MHz, CDCl ) d 159.68,
3
47.35, 135.52, 135.06, 130.13, 127.50, 127.15, 126.67, 125.88, 123.05, 120.73, 114.26,
5.29, 15.95; IR (KBr): 3123, 2967, 2924, 1612, 1476, 1439, 1253, 1176, 1028, 836, 797,
ꢁ
1
þ
88, 536 cm ; HRMS Calcd for [C H N OS] : 298.1009, Found: 298.1011.
1
6
16 3

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7
Compound 2i:
ꢀ
1
Dark brown solid; mp 76–77 C; H NMR (400 MHz, CDCl ) d 8.04 (s, 1H), 7.77 (dd,
3
J ¼ 3.0, 1.2 Hz, 1H), 7.52 (dd, J ¼ 5.0, 1.2 Hz, 1H), 7.48–7.44 (m, 2H), 7.44–7.41 (m,
1
3
1
(
H), 7.41–7.39 (m, 1H), 7.31 (ddd, J ¼ 8.0, 7.3, 1.5 Hz, 1H), 2.37 (s, 3H); C NMR
100 MHz, CDCl ) d 143.62, 135.29, 135.10, 131.48, 130.20, 127.42, 126.65, 126.31,
3
1
7
25.84, 125.83, 121.34, 15.86; IR (KBr): 3429, 3091,2921,1586, 1481, 1429, 1043, 803,
ꢁ
1
þ
57, 620 cm ; HRMS Calcd for [C H N S ] : 274.0467, Found: 274.0471.
1
3
12 3 2
Funding
We are grateful for the financial support provided by the National Natural Science Foundation of
China (Grant Nos. 21662020 and 21764008).
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