Cesium-catalyzed highly regioselective synthesis of (Z)-vinylic selenosulfides via thioselenation of alkynes with unsymmetrical diorganoyl dichalcogenides

Article abstract of DOI:10.1016/j.tet.2017.04.009

A novel one-pot approach for the synthesis of (Z)-vinylic selenosulfides is demonstrated through the thioselenation of a wide range of alkynes with unsymmetrical diorganoyl dichalcogenides (RSSePh) catalyzed by cesium hydroxide monohydrate, avoiding the use of the transition metal catalyst and the previous preparation of chalcogen alkynes. Other outstanding features include mild reaction conditions, high regio- and stereo-selectivity, excellent yields and wide functional group tolerance.

Full text of DOI:10.1016/j.tet.2017.04.009

Accepted Manuscript
Cesium-catalyzed highly regioselective synthesis of (Z)-vinylic selenosulfides via
thioselenation of alkynes with unsymmetrical diorganoyl dichalcogenides
Lifen Peng, Rongzhen Li, Zilong Tang, Jingyang Chen, Rongnan Yi, Xinhua Xu
PII:
S0040-4020(17)30381-2
10.1016/j.tet.2017.04.009
TET 28610
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 2 February 2017
Revised Date: 1 April 2017
Accepted Date: 6 April 2017
Please cite this article as: Peng L, Li R, Tang Z, Chen J, Yi R, Xu X, Cesium-catalyzed highly
regioselective synthesis of (Z)-vinylic selenosulfides via thioselenation of alkynes with unsymmetrical
diorganoyl dichalcogenides, Tetrahedron (2017), doi: 10.1016/j.tet.2017.04.009.
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ACCEPTED MANUSCRIPT
Graphical Abstract
A novel one-pot approach for the synthesis of (Z)-vinylic selenosulfides is demonstrated
through the thioselenation of a wide range of alkynes with unsymmetrical diorganoyl
dichalcogenides (RSSePh) catalyzed by cesium hydroxide monohydrate, avoiding the use of the
transition metal catalyst and the previous preparation of chalcogen alkynes. Other outstanding
features include mild reaction conditions, high regio- and stereo-selectivity, excellent yields and
wide functional group tolerance.

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Cesium-catalyzed highly regioselective
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Tetrahedron
journal homepage: www.elsevier.com
Cesium-catalyzed highly regioselective synthesis of (Z)-vinylic selenosulfides via
thioselenation of alkynes with unsymmetrical diorganoyl dichalcogenides
Lifen Penga, Rongzhen Lia, Zilong Tanga,*, Jingyang Chenb, Rongnan Yib and Xinhua Xub,*
aKey Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan
University of Science and Technology, Xiangtan 411201, P. R. China.
bState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R.
China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A novel one-pot approach for the synthesis of (Z)-vinylic selenosulfides is demonstrated through
the thioselenation of a wide range of alkynes with unsymmetrical diorganoyl dichalcogenides
(RSSePh) catalyzed by cesium hydroxide monohydrate, avoiding the use of the transition metal
catalyst and the previous preparation of chalcogen alkynes. Other outstanding features include
mild reaction conditions, high regio- and stereo-selectivity, excellent yields and wide functional
group tolerance.
Available online
Keywords:
Thioselenation
2009 Elsevier Ltd. All rights reserved
.
(Z)-Vinylic selenosulfide
Unsymmetrical diorganoyl dichalcogenide
Cesium hydroxide monohydrate
Terminal alkyne
1. Introduction
polarity, and only diaromatic dichalcogenide derivatives were
described in this thioselenation. Later, Zeni’s group reported an
efficient route to (Z)-vinylic selenosulfides via thioselenation of
Owing to their useful biological activities and regio-, chemo-
stereo-selectivity, organochalcogen compounds have become
attractively synthetic goal in organic chemistry,1 especially for
the preparation of tri- and tetra-substituted alkenes, which are
main framework for lots of natural products such as Nileprost
analogues2 and Ratjadone,3 as well as drugs such as Tamoxifen4
and Roaccutane5 (Scheme 1). Among these organochalcogen
compounds, vinylic selenides, vinylic sulfides and vinylic
selenosulfide are the most versatile intermediates.6 In spite of the
great success achieved so far in this area,7 some important
challenges still remain. Harsh reaction conditions,8 limited
functional group compatibility,9 and low regio- and srereo-
selectivity10 for the generation of vinnylic selenosulfides and the
requisite use of expensive precious metal catalysts11 or effluvial
reagents12 are some drawbacks of the stated methods.
propargylic
alcohols
with
unsymmetrical
diorganoyl
dichalcogenides (RSSePh) in the presence of 3.0 equivalent of n-
butyllithium (Scheme 2, c).17 This method is only suitable for
propargylic alcohols, and the reaction must be performed under
strict anhydrous conditions. In our previous work, we reported
an one-pot thioselenation of alkynes with a binary system of
diaryl disulfides and diaryl diselenides for highly regio-selective
synthesis of (Z)-vinylic selenosulfides (Scheme 2, d).6i Even
though the desired product was obtained in high regio-
selectivity, purification is still a problem because of the similar
polarity of stereo-isomers of (Z)-vinylic selenosulfides.
Therefore, it is necessary to develop a new procedure to (Z)-
vinylic selenosulfides regio-, chemo- and stereo-selectively
under mild reaction conditions and easy purification. Here, we
report our work on developing an efficient route to (Z)-vinylic
selenosulfides via an exclusive thioselenation of terminal
alkynes with unsymmetrical diorganoyl dichalcogenides
(RSSePh) catalyzed by cesium hydroxide under mild conditions
(Scheme 2, e).
Comparing to vinylic selenides and vinylic sulfides, vinylic
selenosulfides containing both C-S and C-Se on the same double
bond present especial activities, which make it can be more
useful candidate materials for drug development.6i,13 Many
procedures for the synthesis of vinylic selenosulfides have been
reported.14 Thioselenation of alkynes is one of the most efficient
methods for preparation of vinylic selenosulfides.15 The
thioselenation of terminal alkynes using diaryl disulfides and
During illustrating the mechanism of the thioselenation of
alkynes with a binary system of diaryl disulfides and diaryl
diselenides (Scheme 1, d), we found that the unsymmetrical
diorganoyl dichalcogenides (RSSeR’) forming from an exchange
reaction of diaryl disulfides and diaryl diselenides played as the
active and pratical reactants during the thioselenation. What
diaryl
diselenides
as
chalcogenide
reagents
under
photoirradiation16a or hν14e were reported (Scheme 2, a and b).
However, products were obtained as a mixture of (E)- and (Z)-
isomers, which were difficult to be purified due to their similar

2
Tetrahedron
ACCEPTED MANUSCRIPT
intrigues us is that what happens if 3-benzyloxy-1-propylene
entries 5-8), and found that DMF is the most suitable solvent for
1a was treated with diphenyl selenosulfide 2a directly in the
presence of CsOH-H2O. Excitedly, (Z)-vinylic selenosulfide was
obtained as the unique product, and no isomers could be detected
the thioselenation. We also examined the minimum amount of
CsOH-H2O required to promote the reaction (Table 1, entries 9-
13), and the results showed that the use of 20 mol% of CsOH-
H2O is enough to promote the reaction effectively extending the
reaction time to 15 h at rt, giving the corresponding product in
92% yield (Table 1, entry 12). The yields of desired product
reduced to 38% and 54% respectively, when the reaction was
conducted at 0 °C and 50 °C (Table 1, entry 14, 15). By
performing the reaction under air, desired product was obtained
in poor yield and by-products were detected (Table 1, entry 16).
Thus, after carefully analyzing the reaction conditions, the
optimum conditions are 0.2 mmol of alkynes 1, 0.2 mmol of
unsymmetrical diorganoyl dichalcogenides 2, 20 mol% of
CsOH-H2O in DMF at rt under nitrogen for 15 h.
1
by H NMR analysis of the crude product. The unique product
was purified easily via flash column chromatography, avoiding
the complicated purification of the stereo-isomers as other
methods.
Table 1 Optimization of the reaction conditions.a
Scheme 1 Bioligically active compounds containing tetra-
substituted olefins.
a Reaction conditions: 3-benzyloxy-1-propylene 1a (0.2 mmol),
diphenyl selenosulfide 2a (0.2 mmol), solvent (2.0 mL). b GC
yields. c Isolated yields.
To demonstrate the efficiency of this reaction, we explored
the generality of our method extending the conditions to various
terminal alkynes and unsymmetrical diorganoyl selenosulfides,
and the results are summarized in Table 2 and Table 3.
Analyzing Table 2, we observed that the reaction worked well
for various terminal alkynes. Both propargyl alcohols
(substituted propargyl alcohols) and phenylacetylenes gave the
corresponding products in good to excellent yields. The
functional groups substituted to propargyl alcohols influence the
thioselenation slightly (3a-3g, 79%-92%). However, desired
product 3e was obtained in lower yield, mainly due to the large
steric hindrance of the naphthyl. A closer inspections of the
results revealed that the reaction is not sensitive to the nature of
functional groups presenting at the o, m or p positions of the
phenylacetylenes. Both electron-donating and electron-
withdrawing functional groups presenting at the o, m or p
positions of the phenylacetylenes gave the desired products in
excellent yields (3h-3p, 80%-95%). Unfortunately, no desire
product was detected when n-pentyne was treated with 1.0 equiv.
of diphenyl selenosulfide under the optimal conditions (Table 1,
3q), mainly due to the lack of the interaction of the electron-rich
groups (oxygen atom or aromatic ring) with the cesium cation in
the cesium intermediate forming during the thioselenation.
Scheme 2 General methods for synthesis of (Z)-vinylic
selenosulfides.
2. Results/Discussion
We initiated our studies with the thioselenation of 3-
benzyloxy-1-propylene 1a and diphenyl selenosulfide 2a in the
presence of 25 mol% CsOH-H2O. In our studies, 3-benzyloxy-1-
propylene 1a (0.2 mmol) was added to a solution of CsOH-H2O
in THF (2.0 mL) at rt, under nitrogen, and stirred for 0.5 h, then
diphenyl selenosulfide 2a (0.2 mmol) was added to the mixture
solution and stirred at rt for another 10 h. The desired product 3a
was obtained in the yield of 71% (Table 1, entry 4). After
systematic study on the influence of catalysts on the reaction
(Table 1, entries 1-4), we found that CsOH-H2O is the best
catalyst. Then we explored the influence of the solvents such as
DCM, HMPA, 1,4-dioxane and DMF to the reaction (Table 1,
In addition, the reactions are suitable for both alkyl-phenyl
selenosulfide (RSSePh) and aryl-phenyl selenosulfide
(ArSSePh), affording the corresponding products in good to

3
excellent yields. A closer inspection of the results revealed that
Table 3 The thioselenation of alkynes with unsymmetrical
ACCEPTED MANUSCRIPT
diorganoyl selenosulfides.a
the reaction is not sensitive to the nature of functional groups
presenting at the o and p position of the diaryl selenosulfide. The
thioselenations of diaryl selenosulfide with both electron-
donating groups (eg. o-NH2, p-Me, p-OMe) and electron-
withdrawing groups (Cl) gave the corresponding products in
excellent yields (3p, 3r-3t, 85%-90%). The reaction is also
suitable for the thioselenation of alkynes with pyridyl phenyl
selenosulfide, affording the corresponding product in the yield of
87% (3u). In order to explore the scope of the thioselenation
further, some cross reactions were performed under the optimal
conditions, and all the the reactions gave the corresponding
products in good to excellent yields (3v-3ae, 76%-91%). The
configuration of product 3z was determined by examining its
NOESY H-H interaction (SI), and the result show that the
thioselenation of alkynes with unsymmetrical diorganoyl
dichalcogenide occurs stereoselectively to give exclusively Z-
isomer.
Table 2 The thioselenation of various alkynes with diaryl
selenosulfide.a
R
H
CsOH-H2O, 20 mol%
+ PhSSePh
H
R
DMF, rt, N2, 15 h
PhS
SePh
1
2
3
H
H
H
HO
Se
HO
Se
MeO
Se
S
S
S
3b, 86%
3a, 90%
3c, 90%
H
H
H
Se
PhO
Se
(
-Naphth)O
BnO
Se
S
S
S
3e, 79%
3d, 86%
3f, 92%
(n-Pr)
H
H
H
a
Reaction conditions: Alkynes 1 (0.2 mmol), unsymmetrical
AcO
Se
Se
Se
diorganoyl selenosulfides 2 (0.2 mmol), CsOH-H2O (0.04
S
S
S
mmol), DMF (2.0 mL), rt, under nitrogen, 15 h. b Isolated yield.
The method can be carried out on a larger scale, and the
yields of desired products decrease only slightly comparing with
that of small scale. The thioselenation of propargyl alcohol 1a
(112 mg, 2.0 mmol) and diphenyl selenosulfide 2a (530 mg, 2.0
mmol) using CsOH-H2O (66.8 mg, 0.4 mmol) affords (Z)-3-
phenylseleno)-2-(phenylthio)prop-2-en-1-ol 3a (0.571 mg) in
89% yield (90% in 20 mmol scale) (Scheme 3).
3h, 91%
3g, 85%
3i, 90%
Cl
F
H
H
H
H2N
Se
Se
Se
S
S
S
3k, 93%
3j, 95%
3l, 83%
MeO
H2N
H
H
H
Se
Se
Se
S
S
S
Scheme 3 Larger-scale synthesis of 3a.
3m, 80%
3n, 85%
3o, 92%
On the basis of our previous work,6i in which we studied the
mecahnism systematically via control experiments and
theoretical calculation, a mechanism is proposed as depicted in
Scheme 4. The first step of the thioselenation is the generation of
the cesium intermediate A by the removal of acid hydrogen from
terminal alkyne 1 in the presence of CsOH-H2O. Second,
unsymmetrical diorganoyl selenosulfides 2 react readily with
cesium intermediate A, giving species B and C. Finally, there is
nucleophilic addition of specie C with B to give cesium
intermediate D and hydrogen addition by water to give the
desired products 3.
Cl
H
H
Se
Se
S
S
H2N
3q, n.d
3p
, 88%
a
Reaction conditions: Alkynes 1 (0.2 mmol), unsymmetrical
diorgano selenosulfides 2 (0.2 mmol), CsOH-H2O (0.04 mmol),
DMF (2.0 mL), rt, under nitrogen, 15 h. b Isolated yield.

4
Tetrahedron
2H), 3.26 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 133.75,
R
H
ACCEPTED MANUSCRIPT
R
H
R'S
SePh
133.32, 133.23, 130.40, 130.02, 129.95, 129.41, 129.19, 127.84,
1
3
CsOH-H2
O
127.01, 74.99, 58.13.
H2
O
H2O
3d:6i 1H NMR (400 MHz, CDCl3): δ 7.46-7.44 (m, 2H), 7.38-
7.36 (m, 2H), 7.32 (s, 1H), 7.26-7.24 (m, 5H), 7.19-7.15 (m,
3H), 6.87 (t, J = 7.6 Hz, 1H), 6.45 (d, J = 8.0 Hz, 2H), 4.46 (s,
2H); 13C NMR (100 MHz, CDCl3): δ 158.13, 134.73, 133.08,
132.98, 130.38, 130.10, 129.50, 129.43, 129.28, 128.40, 127.80,
127.22, 121.31, 115.01, 70.61.
R
Cs
SePh
R
CCs
R'S
D
A
R'SSePh
2
3e:6i 1H NMR (400 MHz, CDCl3): δ 7.68-7.62 (m, 2H), 7.56
(d, J = 8.0 Hz, 1H), 7.45-7.40 (m, 4H), 7.36-7.32 (m, 2H), 7.26
(t, J = 7.6 Hz, 3H), 7.20-7.18 (m, 4H), 7.04-7.01 (m, 1H), 6.92
(s, 1H), 4.58 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 156.02,
135.05, 134.41, 133.14, 133.03, 130.36, 130.21, 129.53, 129.43,
129.35, 129.23, 128.26, 127.83, 127.70, 127.32, 126.84, 126.47,
123.92, 118.87, 107.55, 70.63.
R
SePh
C
R'SCs
B
R'SCs
B
Scheme 4 Proposed mechanism of the thioselenation.
3. Conclusion
1
In conclusion, we have developed a novel method for the
synthesis of (Z)-vinylic selenosulfides from alkynes and
unsymmetrical diorganoyl dichalcogenides catalyzed by cesium
3f: H NMR (400 MHz, CDCl3) δ 7.52-7.49 (m, 2H), 7.33-
7.31 (m, 2H), 7.24-7.15 (m, 12H), 4.39 (s, 2H), 3.94 (s, 2H); 13
C
NMR (100 MHz, CDCl3) δ137.87, 133.76, 133.31, 133.09,
130.42, 130.27, 130.11, 129.61, 129.37, 129.13, 128.40, 127.76,
127.70, 126.98, 72.54, 72.19; HRMS calc. for C22H20OSSe
412.0400, found 412.0409.
hydroxide monohydrate.
A broad range of alkynes and
unsymmetrical diorganoyl dichalcogenides were tolerated in this
method, and all the (Z)-vinylic selenosulfides could be obtained
in good to excellent yields. Due to the mild reaction conditions,
high stereo-selectivity and excellent yields, this work provides a
convenient way to prepare these important chalcogenide alkenes.
1
3g: H NMR (400 MHz, CDCl3): δ 7.60-7.58 (m, 2H), 7.41-
7.39 (m, 2H), 7.34-7.32 (m, 6H), 7.26-7.24 (m, 1H), 4.60 (s,
2H), 1.98 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 170.47,
137.57, 133.28, 132.94, 130.06, 129.45, 129.20, 128.02, 127.79,
127.18, 66.72, 20.83; HRMS calc. for C17H16O2SSe 364.0036,
found 364.0043.
3h:6i 1H NMR (400 MHz, CDCl3) δ 7.64-7.61 (m, 2H), 7.49-
7.44 (m, 3H), 7.33-7.32 (m, 3H), 7.26-7.24 (m, 2H), 7.18 (t, J =
7.6 Hz, 2H), 7.10-7.08 (m, 1H), 7.02-7.04 (m, 2H), 2.50 (t, J =
8.0 Hz, 2H), 1.58-1.55 (m, 2H), 0.89 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 142.40, 136.51, 134.88, 134.72,
133.29, 132.23, 130.96, 129.46, 128.96, 128.56, 128.19, 127.92,
126.62, 125.95, 37.70, 24.40, 13.87.
3i:6i 1H NMR (400 MHz, CDCl3): δ 7.56-7.55 (m, 2H), 7.40-
7.36 (m, 3H), 7.25 (s, 3H), 7.19-7.17 (m, 2H), 7.12-7.09 (m,
2H), 7.03-6.95 (m, 3H), 2.19 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 137.54, 136.23, 134.66, 134.55, 132.37, 130.97,
129.45, 129.15, 128.94, 128.31, 126.67, 125.99, 21.14.
3j:6i 1H NMR (400 MHz, CDCl3): 7.55-7.53 (m, 2H), 7.42-
7.38 (m, 2H), 7.33 (s, 1H), 7.25-7.23 (m, 3H), 7.16-7.09 (m,
4H), 7.02-6.99 (m, 1H), 6.83-6.78 (m, 2H); 13C NMR (100 MHz,
CDCl3): 163.40, 160.94, 135.04, 134.98, 133.27, 131.38, 131.06,
130.59, 129.41, 128.91, 128.48, 128.42, 128.34, 127.95, 126.81,
126.20, 115.33, 115.11.
4. Experimental
Solvents, reagents, and cesium hydroxide were purchased as
reagent grade and used without further purification.
Unsymmetrical diorganoyl dichalcogenides (RSSeR’) were
synthesized according to literature procedures.18 1H NMR and
13C NMR spectra were recorded using residue solvent peaks as
internal standards (CHCl3, δ = 7.26 ppm for 1H; CDCl3, δ = 77.0
ppm for 13C). Coupling constants are given in hertz. High
resolution mass spectra (HRMS) were measured on an
electrospray ionization (ESI) apparatus using time-of-flight
(ToF) mass spectrometry.
General Procedure for the preparation of (Z)-vinylic
selenosulfides 3a-3ae: Alkyne (0.2 mmol) was added, under
nitrogen, to a solution of cesium hydroxide monohydrate (0.04
mmol) in DMF (2.0 mL). The resulting solution was stirred for
30 min at room temperature. After this time, unsymmetrical
diorgano dichalcogenides (0.2 mmol) was added to the mixture
solution under nitrogen. The reaction was stirred at room
temperature, under nitrogen for 15 hours. After this time, the
mixture was diluted with water (3.0 mL), and extracted with
diethyl ether (3.0 mL × 3). The combined organic phase was
dried over Na2SO4, and concentrated under vacuum. The residue
was purified by flash chromatography on silica gel (eluent
hexane/ethyl acetate) to afford 3a-3ae.
1
3k: H NMR (400 MHz, CDCl3): δ 7.64 (s, 2H), 7.50-7.45
(m, 3H), 7.35 (s, 3H), 7.25-7.17 (m, 6H), 7.13-7.09 (m, 1H); 13
C
NMR (100 MHz, CDCl3): δ 137.37, 136.36, 133.98, 133.43,
133.37, 131.14, 130.56, 129.51, 129.03, 128.57, 128.46, 128.12,
127.97, 126.31; HRMS calc. for C20H15ClSSe 401.9748, found
401.9759.
3l:6i 1H NMR (400 MHz, CDCl3) δ 7.65-7.62 (m, 2H), 7.53 (s,
1H), 7.36-7.34 (m, 3H), 7.26-7.25 (m, 2H), 7.20 (m, 2H), 7.12-
7.10 (m, 1H), 7.03 (t, J = 7.6 Hz, 1H), 6.98-6.96 (m, 1H), 6.89 (t,
J = 2.0 Hz, 1H), 6.55-6.52 (m, 1H), 3.61 (s, 2H); 13C NMR (100
MHz, CDCl3) δ 146.33, 140.12, 135.73, 134.64, 133.23, 132.10,
130.82, 129.35, 129.23, 128.86, 127.99, 127.84, 125.85, 117.89,
114.54, 113.34.
3a:6i 1H NMR (400 MHz, CDCl3) δ 7.60-7.59 (m, 2H), 7.41-
7.30 (m, 2H), 7.33-7.30 (m, 6H), 7.26-7.23 (m, 1H), 4.13 (s,
2H), 1.89 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 133.86,
133.31, 133.02, 132.73, 130.20, 129.87, 129.45, 129.32, 127.96,
127.13, 65.94.
3b:6i 1H NMR (400 MHz, CDCl3): δ 7.59 (s, 1H), 7.55-7.54
(m, 2H), 7.37-7.35 (m, 2H), 7.30-7.26 (m, 5H), 7.18-7.14 (m,
1H), 2.27 (s, 1H), 1.43 (s, 6H); 13C NMR (100 MHz, CDCl3): δ
138.48, 137.35, 134.71, 133.36, 130.50, 129.46, 129.19, 127.97,
127.35, 125.98, 75.88, 29.40.
3c:6i 1H NMR (400 MHz, CDCl3): δ 7.57-7.56 (m, 2H), 7.38-
7.36 (m, 2H), 7.30-7.26 (m, 5H), 7.22-7.21 (m, 2H), 3.89 (s,
3m:6i 1H NMR (400 MHz, CDCl3) δ 7.64-7.62 (m, 2H), 7.37-

5
7.31 (m, 6H), 7.24-7.17 (m, 4H), 7.11-7.09 (m, 1H), 6.54 (d, J =
130.46, 129.41, 129.26, 128.63, 127.91, 127.44, 75.33, 38.76,
29.14; HRMS calc. for C18H20OSSe 364.0400, found 364.0407.
ACCEPTED MANUSCRIPT
8.8 Hz, 2H), 3.66 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
146.02, 144.99, 134.81, 135.05, 131.15, 129.28, 128.78, 128.25,
127.94, 127.62, 125.78, 118.86, 117.91, 114.78.
3y:6i 1H NMR (400 MHz, CDCl3) δ 7.59 (s, 1H), 7.55-7.54
(m, 2H), 7.32-7.24 (m, 7H), 2.12 (s, 1H), 1.43 (s, 6H); 13C NMR
(100 MHz, CDCl3) δ 138.02, 137.96, 133.38, 133.23, 131.72,
130.15, 129.47, 129.24, 128.50, 128.07, 75.79, 29.32.
3n:6i 1H NMR (400 MHz, CDCl3) δ 7.55-7.53 (m, 2H), 7.38
(d, J = 7.2 Hz, 2H), 7.29 (s, 1H), 7.25-7.23 (m, 3H), 7.17-7.15
(m, 2H), 7.09 (t, J = 8.0 Hz, 2H), 7.00 (t, J = 7.6 Hz, 1H), 6.66
(d, J = 8.8 Hz, 2H), 3.64 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
159.09, 134.47, 133.09, 132.95, 131.97, 131.51, 130.84, 129.30,
128.81, 128.19, 127.89, 127.73, 125.87, 113.64, 55.14.
3o:6i 1H NMR (400 MHz, CDCl3): δ 7.58-7.56 (m, 2H), 7.48-
7.45 (m, 3H), 7.28-7.27 (m, 3H), 7.19-7.09 (m, 7H), 7.04-7.00
(m, 1H); 13C NMR (100 MHz, CDCl3): δ 139.00, 135.73, 134.48,
133.37, 132.35, 130.85, 129.50, 128.98, 128.45, 128.38, 128.01,
127.68, 126.82, 126.10.
1
3z: H NMR (400 MHz, CDCl3) δ 7.54-7.52 (m, 2H), 7.40-
7.38 (m, 2H), 7.31-7.25 (m, 6H), 6.96 (s, 1H), 4.06 (s, 2H), 3.91
(s, 2H), 3.29 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 137.70,
133.07, 131.09, 131.04, 130.56, 129.29, 129.00, 128.49, 127.65,
127.21, 75.90, 57.79, 36.55; HRMS calc. for C17H18OSSe
350.0244, found 350.0250.
1
3aa: H NMR (400 MHz, CDCl3) δ 7.60-7.58 (m, 2H), 7.34-
7.26 (m, 8H), 3.90 (s, 2H), 3.29 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 134.88, 133.23, 132.98, 131.89, 131.15, 130.10,
129.42, 129.36, 129.28, 127.93, 74.98, 58.10; HRMS calc. for
C17H17ClOSSe 383.9854, found 383.9861.
1
3p: H NMR (400 MHz, CDCl3) δ 7.62-7.00 (m, 2H), 7.31-
7.30 (m, 3H), 7.23-7.21 (m, 1H), 7.16-7.10 (m, 2H), 7.05-6.97
(m, 3H), 6.92 (s, 1H), 6.57 (d, J = 8.0 Hz, 1H), 6.44 (t, J = 8.0
Hz, 1H), 4.34 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 148.88,
137.70, 136.41, 133.26, 132.95, 132.66, 131.30, 130.87, 130.47,
129.60, 129.43, 129.41, 128.81, 127.69, 125.98, 117.91, 114.73,
114.17; HRMS calc. for C20H16ClNSSe 416.9857, found
416.9868.
1
3ab: H NMR (400 MHz, CDCl3) δ 7.77-7.71 (m, 4H), 7.64-
7.62 (m, 1H), 7.48-7.41 (m, 5H), 7.36-7.31 (m, 5H), 7.20 (s,
1H), 7.13-7.10 (m, 1H), 7.03 (s, 1H), 4.57 (s, 2H), 4.11 (s, 2H);
13C NMR (100 MHz, CDCl3) δ 156.04, 137.71, 134.41, 133.69,
132.96, 132.87, 129.50, 129.44, 129.34, 129.29, 129.19, 129.05,
128.59, 127.67, 127.35, 126.81, 126.42, 123.86, 118.80, 107.58,
72.06, 37.15; HRMS calc. for C26H22OSSe 462.0557, found
462.0568.
1
3r: H NMR (400 MHz, CDCl3): δ 7.59-7.56 (m, 2H), 7.32-
7.27 (m, 10H), 7.25 (s, 1H), 7.24-7.09 (m, 2H), 4.45 (s, 2H),
3.99 (s, 2H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
137.93, 137.28, 133.01, 132.07, 131.15, 130.91, 130.68, 130.59,
129.90, 129.35, 128.38, 127.78, 127.70, 127.67, 72.39, 72.09,
21.15; HRMS calc. for C23H22OSSe 426.0557, found 426.0568.
3s: 1H NMR (400 MHz, CDCl3): δ 7.58-7.56 (m, 2H), 7.40 (d,
J = 8.8 Hz, 2H), 7.41-7.28 (m, 8H), 7.07 (s, 1H), 6.83 (d, J = 8.8
Hz, 2H), 4.41 (s, 2H), 3.95 (s, 2H), 3.78 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 159.60, 137.95, 133.87, 132.94, 132.46, 130.71,
129.86, 129.36, 128.39, 127.81, 127.68, 123.23, 114.72, 72.18,
71.97, 55.39; HRMS calc. for C23H22O2SSe 442.0506 found
442.0512.
1
3ac: H NMR (400 MHz, CDCl3) δ 7.76-7.70 (m, 2H), 7.65
(d, J = 8.4 Hz, 1H), 7.52 (d, J = 7.2 Hz, 2H), 7.47 (s, 1H), 7.45-
7.34 (m, 4H), 7.29-7.27 (m, 5H), 7.09 (dd, J1 = 9.2 Hz, J2 = 1.6
Hz, 1H), 7.00 (s, 1H), 4.64 (s, 2H); 13C NMR (100 MHz, CDCl3)
δ 155.88, 136.55, 134.32, 133.24, 133.07, 131.22, 129.53,
129.43, 129.41, 129.20, 127.94, 127.66, 126.77, 126.49, 123.93,
118.74, 107.48, 70.68; HRMS calc. for C25H19ClOSSe 482.0010,
found 482.0016.
1
3ad: H NMR (400 MHz, CDCl3) δ 7.78-7.69 (m, 4H), 7.63
(d, J = 7.2 Hz, 1H), 7.52-7.50 (m, 2H), 7.37-7.33 (m, 1H), 7.27-
7.26 (m, 2H), 7.18-7.17 (m, 3H), 4.76 (s, 2H), 2.87 (t, J = 7.6
Hz, 2H), 1.76-1.69 (m, 2H), 1.05 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 156.10, 134.42, 132.93, 132.85, 132.06,
129.56, 129.45, 129.35, 129.30, 127.68, 127.63, 126.81, 126.47,
123.89, 118.89, 107.46, 71.47, 34.71, 23.56, 13.47; HRMS calc.
for C22H22OSSe 414.0557, found 414.0562.
1
3t: H NMR (400 MHz, CDCl3): δ 7.52-7.49 (m, 2H), 7.33-
7.31 (m, 2H), 7.24-7.15 (m, 11H), 4.39 (s, 2H), 3.94 (s, 2H); 13
C
NMR (100 MHz, CDCl3): δ 137.87, 133.76, 133.31, 133.09,
130.42, 130.27, 130.11, 129.61, 129.37, 129.13, 128.40, 127.76,
127.70, 126.98, 72.54, 72.19; HRMS calc. for C22H19ClOSSe
446.0010, found 446.0021.
1
3ae: H NMR (400 MHz, CDCl3) δ 7.41-7.39 (m, 2H), 7.31-
1
3u: H NMR (400 MHz, CDCl3): 8.43 (d, J = 8.8 Hz, 1H),
7.29 (m, 2H), 7.19-7.14 (m, 5H), 7.04 (s, 1H), 2.83 (t, J = 8.0
Hz, 2H), 1.79-1.70 (m, 2H), 1.03 (t, J = 8.0 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 139.13, 138.40, 132.86, 130.84, 130.34,
129.08, 128.40, 128.36, 126.56, 125.35, 36.40, 23.95, 13.21;
HRMS calc. for C17H17ClSSe 367.9905, found 367.9914.
7.57-7.49 (m, 4H), 7.30-7.24 (m, 9H), 7.04-7.00 (m, 1H), 4.55
(s, 2H), 4.21 (s, 2H); 13C NMR (100 MHz, CDCl3): 157.50,
150.02, 137.92, 137.80, 136.79, 133.23, 130.09, 129.40, 128.42,
127.91, 127.78, 127.73, 127.50, 121.87, 120.37, 73.44, 72.41;
HRMS calc. for C21H19NOSSe 413.0353, found 413.0361.
Acknowledgments
3v: 1H NMR (400 MHz, CDCl3) δ 7.52 (s, 2H), 7.38-7.25 (m,
8H), 7.03 (s, 1H), 4.02 (s, 4H), 1.85 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 137.76, 133.48, 133.16, 131.93, 130.34, 129.34,
128.96, 128.60, 127.79, 127.37, 66.58, 36.58; HRMS calc. for
C16H16OSSe 336.0087, found 336.0098.
This work was supported by the National Natural Science
Foundation of China (Nos. 21273068 and 21373003), the
National Natural Science Foundation of Hunan Province
(14JJ7027), and the Fundamental Research Funds for the Central
University, Hunan University.
1
3w6i: H NMR (400 MHz, CDCl3) δ 7.53-7.51 (m, 2H), 7.27-
7.20 (m, 8H), 4.06 (s, 2H), 1.84 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 134.96, 133.31, 133.05, 132.00, 131.63, 130.88,
129.90, 129.45, 129.40, 128.04, 65.92.
Supplementary Material
Original 1H and 13C NMR spectra for all compounds can be
found in supplementary material document.
3x: 1H NMR (400 MHz, CDCl3) δ 7.60 (s, 2H), 7.41-7.39 (m,
2H), 7.33-7.26 (m, 6H), 4.10 (s, 2H), 2.04 (s, 1H), 1.36 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 140.68, 137.65, 134.39, 133.38,

6
Tetrahedron
ACCEPTED MANUSCRIPT
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