Visible light-induced co- or cu-catalyzed selenosulfonylation of alkynes: Synthesis of β-(seleno)vinyl sulfones

Article abstract of DOI:10.1021/acs.joc.9b01626

A visible light-induced Co- or Cu-catalyzed selenosulfonylation of alkynes for the synthesis of β-(seleno)vinyl sulfones is demonstrated. This method utilizes a low-cost cobalt salt or metal copper as the catalysts. The reaction goes through a photoinduced free radical addition of selenosulfonates to alkynes for the 1,2-selenosulfonylation of alkynes under mild conditions.

Full text of DOI:10.1021/acs.joc.9b01626

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Article
Visible light-induced Co or Cu-catalyzed selenosulfonylation
of alkynes: synthesis of #-(seleno)vinyl sulfones
Rong Zhang, Pei Xu, Shun-Yi Wang, and Shun-Jun Ji
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01626 • Publication Date (Web): 02 Sep 2019
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The Journal of Organic Chemistry
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Visible light-induced Co or Cu-catalyzed selenosulfonylation of alkynes: synthesis of
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β-(seleno)vinyl sulfones
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Rong Zhang, Pei Xu, Shun-Yi Wang*, and Shun-Jun Ji*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science,
and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou, 215123, China.
E-mail: shunyi@suda.edu.cn; shunjun@suda.edu.cn
RECEIVED DATE
*CORRESPONDING AUTHOR FAX: 86-512-65880307.
R3
R2
O
Se
R3
R4
R1
R2
or
Co
Cu
+
S
Se
O
R1
O
S
O
R4
R1 = Alkyl, Aryl, Het
32 examples, up to 96% yield
R2 = H, COOR', CONHR', SO2Ar, Ar
without photocatalyst
mild condition
one-step-formation of C-Se and C-S bonds
ABSTRACT. A visible light-induced Co or Cu-catalzyed selenosulfonylation of alkynes for the synthesis
of β-(seleno) vinyl sulfones is demonstrated. This method utilizes a low-costcobalt salt or metal copper
as the catalysts. The reaction goes through a photoinduced free radical addition of selenosulfonates to
alkynes for the 1,2-selenosulfonylation of alkynes under mild conditions.
1. INTRODUCTION
Organic selenium compounds have been widely used in organic synthesis. Among them, vinyl selenides
are valuable synthetic intermediates and therapeutic entities, which have a wide range of biological
activities. Therefore, a plethara of synthetic strategies have been developed for the construction of vinyl
selenide.1 Selenium in organic compounds can be introduced, converted and removed using a variety of
simple ways, which makes the selenization reaction essential.2 Alkynes play a critical role in organic
synthesis due to their easyavailability and accessibility. In 1983, Back et al. first used
azobisisobutyronitrile (AIBN) as a free radical initiator to promote the cleavage of the pre-prepared
PhSeSO2Ph reagent to construct β-(seleno) vinyl sulfone compounds (Scheme 1a).3a In recent years, it
has been reported that multi-component reaction of benzenesulfonyl hydrazide, diselenide and alkyne can
successfully affords β-(seleno) vinyl sulfone compounds under mild conditions through
difunctionalization of alkyne (Scheme 1b).3b,3c Recently, a four-component reaction has been developed
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for the preparation of a broad range of β-(seleno) vinyl sulfones with high levels of regioselectivity and
stereoselectivity through sulfur dioxide insertion utilizing DABSO (Scheme 1c).3d
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Visible light-induced chemical transformations have gained increasing attentions for their crucial
importance in synthetic chemistry. Photoreduction-activated photo-oxidation-reduction catalysis (Ru or
Ir) have been shown to involve the design and development of valuable reactions through a unique single-
electron transfer pathway.4 Nevertheless, the relatively expensive cost of Ru or Ir based photocatalysts
necessitates the development of reactions utilizing inexpensive metals such as copper, cobalt, nickel, etc.
as photocatalysts.5 Selenosulfonates are useful synthons for the construction of organic selenium
compounds. More recently, we have developed a Nickel-catalyzed reductive selenylation of alkyl
bromides with selenosulfonates for the preparation of selenides. As a continuation study on
selenosulfonates and C-S bond formation reactions,6 we herein describe a visible light-induced Co or Cu-
catalzyed of selenosulfonylation of alkynes for the synthesis of β-(seleno) vinyl sulfones (Scheme 1d).
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Scheme 1. Selenosulfonation of Alkynes.
(a) two component reaction:
R1
R4Se
SO2R3
R2
AIBN
+
R3SO2SeR4
R1
R2
(b) three component reaction:
Li's work:
R1
PhSe
SO2Ar
R2
Cu-cat
rt
R1
R2
+
ArSO2NHNH2
+
PhSeSePh
PhSeSePh
Liu's work:
R1
simply mixing
oxidant
R1
PhSe
SO2Ar
R2
R2
+
ArSO2NHNH2
+
(c) four component reaction:
R1
ArSe
SO2Ar
R2
R1
R2
+
ArN2BF4
+
DABSO
+
(ArSe)2
(d) this work:
R1
SO2R3
R2
[Cu] or [Co]
visible light
R3SO2SeR4
R1
R2
+
R4Se
2. RESULTS AND DISCUSSION
We initially selected ethyl 3-phenylpropiolate 1a and PhSeSO2Ph 2a as model substrates for the
optimization of the reaction conditions (Table 1). Gratifyingly, the transformation proceeded smoothly in
the presence of 5 mol% CoCl2 in MeCN under Ar atmosphere irradiated by blue light for 4 hours, giving
ethyl 3-phenyl-3-(phenylselanyl) -2-(phenylsulfonyl)acrylate 3aa in 83% yield (Table 1, entry 1), and the
structure of compound 3aa was unambiguously confirmed by single crystal diffraction(see Supporting
Imformation (SI) for more details). We found the reaction failed to give the desired product 3aa in the
absence of CoCl2 or blue LED (Table 1, entries 2-3). Next, we screened the reaction solvents. The reaction
could give 3aa in a high LC yield of 82% when using THF as the solvent (Table 1, entry 4). Subsequently,
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we found that the yield of reaction was not changed when reaction time prolonged from 4 hours to 8 hours,
even 12 hours (Table 1, entries 5-6). Next, we explored the effects of different transition metal-catalysts
on the reaction. Surprisingly, metal copper could also promote the reaction to furnish 3aa in 50% yield
(Table 1, entry 7). The optimal result was obsreved when CoC2O4 was empolyed as the catalyst, furnishing
3aa in 86% yield (Table 1. entry 8). Therefore, we established the optimum conditions for the reaction of
1a and 2a under the catalysis of 5 mol% CoC2O4, acetonitrile as solvent, under Ar atmosphere irradiated
by blue LED for 4 hours.
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a
Table 1. Optimization of the reaction conditions
O
Et
O
O
Ph Se
Ph
standard condition
Et
+
PhSeSO2Ph
O
O
S
Ph
O
Ph
1a
2a
3aa
entry
conditions
yield (%)b
1
2
3
4
5
6
7
8
standard conditiona
in the absence of CoCl2
without blue LED
83
0
0
THF instead of MeCN
8 h instead of 4 h
12 h instead of 4 h
Cu instead of CoCl2
82c
83
83
50
86
CoC2O4 instead of CoCl2
aReaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), CoCl2 (5 mol%), MeCN (1.0 mL), room temperature, under Ar
and with blue LED, 4 h. bIsolated yield. c LC yield.
With the optimized reaction conditions in hand, we set out to explore the substrate scope of this reaction
using a variety of different reagents, and the results are summarized in Tables 2 (Table 2). We examined
the reactions of various types of alkyne esters react with 2a, under the catalysis of CoC2O4. When using
alkyne esters with less steric hindrance (1a-1b), the desired products 3aa and 3ab were obtained in 86%
and 75% yields, respectively. And the sterically hindered alkyne ester (1c) gave 3ca only in a yield of
39%. Then we investigated the scope of selenosulfonates. When the aryl selenosulfonates were employed,
the target products could be obtained in good yields. When using 2e as raw material, both stereoisomers
of the target product can be isolated and the overall yield can reach 66%. When alkyl selenosulfonates
(2g-2h) were used, the desired products 3ag and 3ah could be afforded in 87% and 76% yields,
respectively. In order to test the large-scale application of the reaction, we conducted the reaction 1a with
2a on 5 mmol scale under standard conditions, the desired product 3aa could also be isolated in 84%
yield.
Table 2. Scope of selenosulfonates with alkyne esters a,b
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O
R2
O
O
R2 Se
R2
+
CoC2O4 (5 mol%)
1
2
O
R3SeSO2R4
O
Ar, MeCN, Blue LED, rt, 4 h
S
O
R3
3
4
1(a-c)
2(a-h)
3aa-3ah
5
6
7
8
OMe
O
Se
O
O
O
O
Se
O
O
Se
O
O
S
O
S
S
O
O
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3aa
(86%. E/Z=75:25)
3ba
(75%, E/Z=50:50)
3ca
(39%, E/Z=70:30)
O
O
O
Se
O
O
Se
O
O
O
Br
Se
O
O
Se
O
O
S
S
O
O
S
S
O
O
Me
Cl
F
3ab
3ac
ad (
3ae
(66%, 62:38)
(70%, 62:38)
O
(80%, 67:33)
O
3
80%, 70:30)
O
O
Se
O
Se
O
O
S
O
O
O
S
Se
S
O
O
3af
3ag
3ah
(76%, 75:25)
(82%, 62:38)
(87%, 90:10)
Ph
Gram-scale synthesis:
Ph COOEt
Se
O
CoC2O4 (5 mol%)
Ar, MeCN, Blue LED, rt, 4 h
PhSeSO2Ph
+
OEt
S O
O
Ph
3aa
(84%)
1a
2a
(5 mmol)
1.98g
aReaction conditions: alkyne 1 (0.2 mmol), 2 (0.2 mmol), CoC2O4 (5.0 mol%), in MeCN (1.0 mL) at room temperature,
under Ar and with blue LED,4 h. bIsolated yield.
After the exploration of the reaction to alkyne esters, we hope to further expand the application of the
reaction. Considering the alkynamides as important functional alkyne, we tried to achieve this reaction
using alkynamide compounds. Therefore, we using alkynamide compounds as the source of alkyne, and
Table 3. Optimization of the reaction conditions.a, b
O
tBu
NH
O
Ph Se
Ph
catalyst
tBu
+
PhSeSO2Ph
N
O
Ar, MeCN, Blue LED, rt
H
S
Ph
O
Ph
1e
2a
3ea
entry
catalysts (mol%)
yield (%)b
1
2
3
4
5
6
7
8
CoCl2 (5)
CuI (5)
CuCl (5)
CuCl2 (5)
Cu(OAc)2 (5)
Cu (5)
55
68
56
44
66
85
87
72
Cu (2)
Cu (1)
aReaction conditions: 1e (0.2 mmol), 2a (0.2 mmol), catalyst, MeCN (1.0 mL), room temperature, under Ar and with blue
LED, 4 h. bIsolated yield.
react under the best condition we mentioned above. Unfortunately, under this reaction condition, the
corresponding target product can only be obtained with an isolated yield of 55% (Table 3. entry 1). Then,
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we explored the reaction conditions and the results are summarized in Table 3. We tried a series of copper
catalysts: including CuI, CuCl, CuCl2, Cu(OAc)2 and Cu, and experimental results shown that the reaction
using copper is the best, the target product can be obtained in an isolated yield of 85% in the presence of
5 mol% copper (Table 3. entries 2-6). Besides, the results shows that higher the valence state, the worse
the catalytic effect. Next, we found that the amount of Cu(0) could be reduced from 5 mol% to 1 mol%
without deteriorate the catalytic effect (Table 3. entry 6-8). After exploring the reaction conditions, we
established that the 1e and 2a were catalyzed by 2 mol% Cu(0) in MeCN, under Ar atmosphere and blue
LED for 4 hours.
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Table 4. Scope of selenosulfonates with alkynamides a,b
R4
O
O
R3 Se
R1
S
R2
Cu (2 mol%)
O
R2
NH
+
R3SeSO2R4
N
H
Ar, MeCN, Blue LED, rt, 4 h
R1
O
2a h
-
1d j
-
3da 3dh
-
O
Se
S
O
O
O
Se
S
Se
S
O
O
tBu
NH
O
NH
NH
O
O
CF3
3da
3ea
3fa
(86%, 67:33)
(87%, 89:11)
(86%, 67:33)
O
O
O
Se
S
Se
S
Se
S
O
tBu
O
O
O
tBu
Se
N
S
O
tBu
NH
NH
NH
NH
O
O
O
O
O
O
O
3ga
3ha (
3ia
3ja
(89%, 86:14)
92%, 62:38)
(88%, 67:33)
(71%, 67:33)
Cl
F
Me
O
Se
S
O
O
tBu
NH
Br
Se
S
O
O
O
tBu
NH
Se
S
Se
S
O
O
tBu
tBu
O
NH
NH
O
O
O
3db
3dc
3dd
3de
(75%, 69:31)
(73%, 81:19)
(78%, 59:41)
(87%, 67:33)
O
O
O
Se
S
Se
S
Se
S
O
tBu
NH
O
tBu
NH
O
tBu
NH
O
O
O
3df
3dg
3dh
(54%, 67:33)
(96%, 60:40)
(45%, 81:19)
Ph
O
O
Ph Se
Ph
S
tBu
Cu (2 mol%)
Ar, MeCN, Blue LED, rt, 4 h
O
tBu
+
PhSeSO2Ph
N
H
NH
Ph
O
2a
1d
3da
(77%)
765.4mg
(2mmol)
aReaction conditions: alkyne 1 (0.2 mmol), 2 (0.2 mmol), Cu (2.0 mol%), in MeCN (1.0 mL) at room temperature, under Ar
and with blue LED,4 h. bIsolated yield.
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Under optimal conditions, we explored the scope of the substrate (Table 4). By comparing 3da and
3ea, we found that the steric hindrance and electronic effect of the group attached to the amide group has
no effect on the reaction. A series of alkynamides bearing both electron-withdrawing groups (R = CF3,
COOMe) and electron-donating groups (R = Me, OMe) reacted smoothly to give the corresponding β-
(seleno)vinyl sulfones in high yields (3fa-3ia). When pyridinamide is used, the reaction shows excellent
heterocyclic tolerance, and the desired product is obtained in 71% yield. Then, we used 1d as a reaction
substrate to expand various selenosulfonates. The halogen-substituted (R = F, Cl, Br) aryl selenate
sulfonate and 1d can obtain the corresponding target product in a higher yield. Besides, the reaction with
a weak electron-donating group (R = Me) could give 3df in a yield of 96%. However, compared to aryl
selenate sulfonate, alkyl selenate sulfonate does not show the excellent reaction effect. When an alkyl
group is bonded to selenium, the reaction can only obtain the corresponding target product in a moderate
yield, and when the sulfonyl group is an alkyl group, the reaction is relatively better. In order to test the
large-scale application of the reaction, we conducted the reaction of 2 mmol 1d with 2a under standard
conditions. The desired product 3da could be observed in 77% yield.
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2
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Table 5. Scope of alkynes with 2aa,b
R2
CoC2O4 or [Cu]
PhSe
R1
R2
+
PhSeSO2Ph
R1
Ar, MeCN, Blue LED, rt, 4 h
SO2Ph
1(k-r)
2a
3ka-3ra
SO2Ph
SePh
PhSe
H
SePh
O
O
S
H
H
H
O
SO2Ph
SePh
SO2Ph
SO2Ph
N
S
3ka
3la
3ma
3na
(89%, 75:25)
catalyst : Cu
(63%, E/Z >99%)
(89%, E/Z >99%)
catalyst : Cu
(71%, E/Z >99%)
catalyst : Cu
catalyst : CoC2O4
O
Ph
Se
SO2Ph
SePh
O
SePh
PhSe
O
O
S
O
O
SO2Ph
SO2Ph
SO2Ph
O
3oa
catalyst : CuI
3pa
(69%, ,50:50)
catalyst : Cu
3qa
(22%, 67:33)
catalyst : Cu
3ra
(60%, 81:19)
(38%, 75:25)
catalyst : CoC2O4
PhSe
Ph
H
Cu (5 mol%)
+
PhSeSO2Ph
Ph
H
Ar, MeCN, Blue LED, rt, 4 h
SO2Ph
1n
2a
3na (83%)
996.2 mg
(3 mmol)
aReaction conditions: alkyne 1 (0.2 mmol), 2 (0.2 mmol), CoC2O4 (5.0 mol%) or [Cu] (2.0 mol%), in MeCN (1.0 mL) at room
temperature, under Ar and with blue LED,4 h. bIsolated yield.
In addition, we tried different types of alkynes, which were carried out under the conditions of cobalt
oxalate and copper catalysis. The experimental results show that the reaction can be carried out and most
of the corresponding target products can be obtained in modorate to good yields (Table 5). Surprisingly,
but-3-yn-1-yl 4-methylbenzenesulfonate (1k) and the terminal alkyne bearing a heterocyclic ring (1l, 1m)
proceeded with high levels of regio- and stereoselectivity. In order to test the large-scale application of
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the reaction, we conducted the reaction of 3 mmol 1n with 2a under standard conditions. The desired
product 3na could be observed in 83% yield.
1
2
3
To gain some insight into the mechanism of this reaction, we conducted several control experiments.
When TEMPO (2.0 equiv.) or ethene-1,1-diyldibenzene 4 (2.0 equiv.) was added to the reaction as a free
radical quenching agent, we can observed that reaction was totally suppressed (Scheme 2, eq. 1 and eq.
6). After that, we try to add 4 when only 2f exists, and 33% yield of compound 5 was obtained (Scheme
2, eq. 2). Based on this, we added CoC2O4 and found that the yield of the compound 5 was increased to
44% (Scheme 2, eq. 3). In order to explore the role of irradation, we perform the reaction in dark. After
eq. 4 and eq. 5 reacted at 40 °C, no reaction was observed. These results indicated that light irradiation
plays a crucial role in Se-S bond cleavage. It was also found that 2 easily splits to generate free radicals
under light conditions, and the metal catalyst has a certain influence on the generation of free radicals.
Then, we tried the reaction of 2a with PhSeSePh and PhSSO2Ph. It was found that 3aa was observed in
55% yield, which indicated that PhSeSePh is an plausible intermediate in the reaction (Scheme 2, eq. 7).
Finally, we desired to figure out if the formation of Cu-alkyne complex activates the alkyne. And result shows that
Cu-alkyne complex is not reaction intermediate (Scheme 2, eq. 8).
4
5
6
7
8
9
10
11
12
13
14
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Scheme 2. Control Experiments
O
TEMPO (2.0 equiv)
O
+
PhSeSO2Ph
N.D
(1)
standard condition
1a
2a
(2)standard condition
(2) 5 (44 %)
(3)
+
+
PhSeSePh
PhSeSePh
O
S
Se
Ph
(3)standard condition without CoC2O4
5
(33 %)
+
O
Ph
(4)Ar, 40 oC, 4 h
(4) N.R
(5) N.R
2f
4
(5)standard condition without visible light
O
Ph
Ph
S
H
Ph
Ph
O
4
5
standard condition
(6)
1a
+
2f
messy
standard condition
1a
+
PhSeSePh
+
PhSSO2Ph
3aa (55%) (7)
Ph
Cu
+
2a
N.R
(8)
Ar, Blue LED, rt, 4 h
Based on the reported literatures3,7 and our experimental results, a plausible mechanisms was proposed
in Scheme 3. Firstly, homolysis of 2 generates sulfonyl radical and seleno radical in the presence of metal
catalyst irradiated by light. The homocoupling of seleno radical gives R3SeSeR3. The sulfonyl radical
reacts with alkynes to form intermediates A. Then intermediate A and metal coordination to form
intermediate B, which in turn interacts with the R3SeSeR3 to form intermediate C and regenerates a seleno
radical. The reductive elimination of intermediate C furnishes product 3 and regenerates the catalyst.
Scheme 3. Plausible Mechanism.
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*
O
O
Se
Se
hv
Homolysis
R3Se
R3SeSeR3
S
S
R3
R3
1
R4
R4
[M]
O
O
2
2
3
[M]
4
5
MeCN
MnLn
R4SO2
3
6
7
8
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R1
R2
SeR3
1
LnMn+2
R2
SO2R4
R1
R2
SO2R4
R1
C
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A
R3Se
LnMn+1
R2
SO2R4
R1
R3SeSeR3
B
3. CONCLUSION
In summary, we reports a new method for the synthesis of β-(seleno)vinyl sulfone by generating free
radicals under light-induced, followed by metal-catalyzed addition to alkyne. Key features of the reaction
include extensive substrate universality, readily available reagents, amenability to gram scale synthesis,
excellent functional group tolerance and heterocyclic tolerance. In addition, the use of inexpensive
transition metals as catalysts in photoreaction is an innovation and breakthrough in a series of previous
experiments which using precious metal catalyzed visible light catalysis.
4. EXPERIMENTAL SECTION
General Experimental Information. Unless otherwise noted, all commercially available compounds were used as provided without further
purification. Solvents for chromatography were analytical grade and used without further purification. Analytical thin-layer chromatography
(TLC) was performed on silica gel, visualized by irradiation with UV light. For column chromatography, 200-300 mesh silica gel was used.
1H-NMR and 13C-NMR were recorded on a BRUKER 400 MHz spectrometer in CDCl3. Chemical shifts (δ) were reported referenced to an
internal tetramethylsilane standard or the CDCl3 residual peak (δ 7.26) for H NMR. Chemical shifts of 13C NMR are reported relative to
1
CDCl3 (δ 77.16). Data are reported in the following order: chemical shift (δ) in ppm; multiplicities are indicated s (singlet), bs (broad singlet),
d (doublet), t (triplet), m (multiplet); coupling constants (J) are in Hertz (Hz). IR spectra were recorded on a BRUKER VERTEX 70
spectrophotometer and are reported in terms of frequency of absorption (cm-1). HRMS spectra were obtained by using BRUKER
MICROTOF-Q III instrument with ESI source.
Information for LED Photoreactor. (1)Blue LEDs: 200 cm strips, 470 nm blue light, 32918 mcd ft-1; (2) Power Supply: 12V DC CPS
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General procedure for the synthesis of reactants
Procedure 1a-1c. A mixture of (0.4 mmol), phenylpropiolic acid (0.6 mmol, 87.6 mg), Cs2CO3 (2 equiv, 260.7 mg), CuI (10 mol%, 7.6 mg),
and CH3CN (2 mL) in a tube was stirred in air at 60 °C oil bath for 24 h. After that the mixture was poured into ethyl acetate, then washed
with water, extracted with ethyl acetate, dried by anhydrous Na2SO4, then filtered and evaporated under vacuum, the residue was purified by
flash column chromatography (petroleum ether or petroleum ether/ethyl acetate) to afford the corresponding coupling products.
Procedure 1d-1j. An oven dried round-bottom flask was charged with phenylpropiolic acid (1 mmol, 146.1 mg) and DMAP (10 mol%, 12.2
mg) and purged with argon for 10 minutes. The contents were dissolved in distilled DCM (0.25 M), and the amine was added (1.1 equiv).
The mixture was cooled to 0 °C and a DCM solution (0.4 M) of DCC (1.0 mmol, 206.3 mg) was added dropwise and the reaction was
warmed to room temperature and stirred overnight (approximately 12 hours). The contents of the flask were filtered through a plug of Celite®
eluting with DCM. The filtrate was concentrated in vacuo while adsorbing onto silica gel and the crude material was purified by flash column
silica gel chromatography using the indicated solvent system.
Procedure 1o. Ethynylbenzene (0.88 mL, 8.0 mmol, 816 mg) was dissolved into THF (8 mL), and the solution was cooled to -78 ºC. To the
solution, n-BuLi (5.0 mL, 8.0 mmol, 1.6 M in hexane) was added. After being stirred for 1 h at -78 ºC, ethyl 3-phenylpropanoate (0.46 mL,
4.0 mmol) and BF3 OEt2 (1.2 mL, 9.6 mmol) were added successively. The reaction was quenched by sat. NH4Cl aq., and extracted three
times with EtOAc. The combined organic layer was dried over Na2SO4, and the solvent was removed under a reduced pressure. The residue
was purified by column chromatography (SiO2, eluent: hexane/EtOAc) to afford the desired ynones 1a in the yield of 62%.
Procedure 1q. A mixture of phenylpropiolic acid (0.5 mmol, 73 mg), PhSO2Na (2 equiv, 164 mg), I2 (0.5 equiv, 63.3 mg), and 70% TBHP
in H2O (3 equiv, 148.5 mg ) in THF (2 mL) was stirred at room temperature (30-32 °C), 16 h. 1q was obtained in the isolated yield of 83%,
after chromatographic purification.
.
Procedure 2a-2h. A mixture of sulfinic acid sodium salt (4 mmol), diselenide (1 mmol,) and NBS (2 mmol, 356 mg) in MeCN was stirred
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The Journal of Organic Chemistry
at room temperature. After the completion of the reaction, as monitored by TLC, the reaction mixture was washed with water and extracted
with ethyl acetate. The organic phase was separated and dried over anhydrous Na2SO4 and filtered. The filtrate was concentrated and the
resulting residue was purified by column chromatography to provide the desired aryl-thiosulfonates.
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1H, 13C spectra data of 1b-1c can refer to published document8a, 8b
.
.
1H, 13C spectra data of 1d-1j can refer to published document8c, 8d
1H, 13C spectra data of 1o can refer to published document8e, 8f
1H, 13C spectra data of 1q can refer to published document8g.
.
1H, 13C spectra data of 2a-2h can refer to published document6a, 8h
.
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General procedure for the synthesis of products 3. Ethyl 3-phenylpropiolate 1a (0.20 mmol, 34.8 mg), PhSeSO2Ph (0.20 mmol, 1.0 equiv,
59.4 mg) CoC2O4 ( 0.05 mmol, 1.5 mg) were added to an oven-dried schlenk reaction tube with a magnetic stir bar. The tube was sealed
with a rubber cap and pumping gas three times under argon. Then MeCN (3.0 mL) were added and resulting mixture was stirred at room
temperature for 4 h. After completion of the reaction, as indicated by TLC, the pure product was obtained by flash column chromatography
using n-hexane on silica gel to afford 3aa in 86% yield. All remaining β-(seleno) vinyl sulfones were prepared using a procedure similar to
that used to synthesize 3aa.
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ethyl 3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)acrylate (3aa) Yield = 86% (81.1 mg, 75 : 25). White solid. 1H NMR (400 MHz, CDCl3)
δ 8.33 (dd, J = 8.4, 1.3 Hz, 1H), 7.61 (dd, J = 14.9, 7.6 Hz, 2H), 7.48 (t, J = 7.4 Hz, 1H), 7.34 (t, J = 7.8 Hz, 1H), 7.14 – 7.01 (m, 3H), 6.95
(dd, J = 7.8, 2.2 Hz, 5H), 6.78 (d, J = 6.8 Hz, 1H), 4.39 (q, J = 7.1 Hz, 1H), 3.84 (q, J = 7.1 Hz, 1H), 1.37 (t, J = 7.1 Hz, 2H), 0.74 (t, J = 7.1
Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 165.4, 163.5, 141.7, 137.0, 136.7, 134.4, 134.0, 133.0, 128.9, 128.9, 128.7, 128.6, 128.6, 128.5,
128.5, 128.4, 128.2, 128.1, 127.8, 127.5, 127.1, 62.8, 62.0, 14.14, 13.3. IR (ATR):  = 1718, 1559, 1440, 1310, 1250, 1149, 1085, 1041, 998,
743, 686, 556 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C23H20O4SSeNa 495.0135 ; Found 495.0127.
phenethyl 3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)acrylate (3ba) Yield =75.3% (82.5 mg, 50 : 50). White solid. 1H NMR (400 MHz,
CDCl3) δ 8.31 (d, J = 7.7 Hz, 1H), 7.66 (dt, J = 43.4, 7.5 Hz, 2H), 7.48 (dd, J = 25.1, 7.4 Hz, 1H), 7.28 (ddd, J = 29.8, 13.7, 7.2 Hz, 5H),
7.11 – 7.01 (m, 3H), 6.99 – 6.89 (m, 6H), 6.85 – 6.80 (m, 1H), 6.75 (d, J = 7.0 Hz, 1H), 4.54 (t, J = 7.4 Hz, 1H), 3.97 (t, J = 7.4 Hz, 1H),
3.07 (t, J = 7.4 Hz, 1H), 2.41 (t, J = 7.4 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 141.6, 136.9, 136.7, 136.5, 134.3, 134.0, 133.0, 129.1,
129.0, 128.9, 128.8, 128.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.4, 128.2, 128.1, 127.6, 127.1, 126.8, 126.6, 67.0, 66.4, 34.9, 34.2. IR
(ATR):  = 1704, 1547, 1477, 1444, 1319, 1253,1238, 1202, 1149, 1084, 1049, 975, 807, 743, 699, 685, 597, 566, 544 cm-1; HRMS (ESI):
[M+H]+ Calcd. for C29H25O4SSe [M+H]+: 549.0634; Found 549.0629.
3-methoxybenzyl 3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)acrylate (3ca) Yield =39.4% (44.4 mg, 70 : 30). White solid. 1H NMR (400
MHz, CDCl3) δ 7.53 (dd, J = 26.3, 7.7 Hz, 2H), 7.42 – 7.37 (m, 1H), 7.31 – 6.72 (m, 16H), 5.54 – 4.76 (m, 2H), 3.88 – 3.66 (m, 3H).
13C{1H}NMR (100 MHz, CDCl3) δ 166.2, 163.2, 159.7, 141.2, 136.8, 136.4, 136.0, 134.1, 132.9, 130.0, 129.5, 129.2, 128.8, 128.7, 128.4,
128.4, 128.3, 128.2, 128.2, 127.9, 127.9, 127.5, 127.4, 126.9, 120.7, 120.6, 114.4, 114.0, 113.6, 68.1, 67.6, 55.2, 55.1. IR (ATR):  = 3054,
2924, 1716, 1541, 1476, 1445, 1319, 1235, 1148, 1085, 1020, 965, 738, 685, 566 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for
C29H24O5SSeNa 587.0402; Found 587.0410.
N-(tert-butyl)-3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)acrylamide (3da) Yield =87.3% (87.1 mg, 89 : 11). White solid. 1H NMR (400
MHz, CDCl3) δ 7.66 – 7.34 (m, 5H), 7.14 – 7.05 (m, 4H), 6.99 – 6.90 (m, 5H), 6.76 (dd, J = 7.9, 1.5 Hz, 2H), 1.42 (s, 8H), 0.93 (s, 1H).
13C{1H}NMR (100 MHz, CDCl3) δ 161.7, 141.2, 137.1, 136.7, 134.8, 133.1, 131.8, 128.9, 128.8, 128.6, 128.5, 128.4, 128.0, 127.5, 126.9,
52.4, 28.6, 27.9. IR (ATR):  = 3349, 2965, 1659, 1532, 1446, 1310, 1220, 1147, 1086, 739, 686, 619, 556 cm-1; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd. for C25H26NO3SSe 500.0793; Found 500.0811.
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N-butyl-3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)acrylamide (3ea) Yield = 86.0% (85.8 mg, 67 : 33). Yellow solid. H NMR (400
MHz, CDCl3) δ 7.48 (t, J = 7.4 Hz, 3H), 7.33 (t, J = 7.8 Hz, 2H), 7.07 (t, J = 8.7 Hz, 3H), 6.90 (dt, J = 21.7, 7.3 Hz, 5H), 6.67 (d, J = 7.1 Hz,
2H), 3.43 (q, J = 6.9 Hz, 2H), 1.64 – 1.58 (m, 2H), 1.42 (q, J = 7.4 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ
162.8, 137.1, 134.9, 133.1, 130.2, 129.5, 128.8, 128.6, 128.3, 127.9, 127.2, 126.8, 40.2, 31.4, 20.3, 13.9. IR (ATR):  = 3368, 2361, 1672,
1526, 1446, 1322, 1285, 1218, 1152, 1081, 809, 686, 548 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C25H26NO3SSe 500.0799; Found
500.0810.
3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)-N-(4-(trifluoromethyl)phenyl)acrylamide (3fa) Yield =86.3% (101.2 mg, 67 : 33). White
solid. 1H NMR (400 MHz, CDCl3) δ 8.44 (d, J = 7.7 Hz, 1H), 7.92 – 7.60 (m, 4H), 7.51 – 7.30 (m, 4H), 7.23 – 7.02 (m, 4H), 6.89 (dt, J =
28.6, 7.3 Hz, 5H), 6.69 (d, J = 7.3 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 172.2, 161.4, 141.3, 140.6, 140.2(d, J F-C = 22.7 Hz) 137.1,
137.1, 136.7, 134.62, 133.49, 130.06, 129.13, 129.07, 128.90, 128.84, 128.74, 128.65, 128.53, 128.32, 128.20, 128.00, 127.32, 126.92,
126.5(q, JF-C = 3.6 Hz), 126.0 (d, J F-C = 3.6 Hz), 120.4, 119.8. IR (ATR):  = 3334, 3062, 2358, 1668, 1538, 1305, 1255, 1145, 1119, 1067,
840, 741, 682, 542 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C28H20F3NO3SSeNa 610.0174; Found 610.0134.
3-phenyl-3-(phenylselanyl)-2-(phenylsulfonyl)-N-(m-tolyl)acrylamide (3ga) Yield = 89.6% (95.4 mg, 86 : 14). White solid. 1H NMR (400
MHz, CDCl3) ) δ 9.63 (s, 1H), 7.54 – 7.44 (m, 5H), 7.36 – 7.26 (m, 3H), 7.11 – 7.00 (m, 4H), 6.92 (dt, J = 14.5, 6.4 Hz, 6H), 6.71 (d, J = 6.8
Hz, 2H), 2.39 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 170.7, 160.8, 141.3, 139.1, 137.1, 134.9, 133.3, 129.3, 129.0, 128.9, 128.9, 128.7,
128.5, 128.4, 128.0, 127.3, 126.8, 126.0, 121.3, 117.8, 21.6. IR (ATR):  = 3335, 3057, 1668, 1544, 1488, 1439, 1304, 1145, 1082, 730, 683,
610, 538 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C28H24NO3SSe 534.0637; Found 534.0611.
N-(tert-butyl)-3-(4-methoxyphenyl)-3-(phenylselanyl)-2-(phenylsulfonyl)acrylamide (3ha) Yield = 92.3% (97.6 mg, 62 : 38). White
solid. 1H NMR (400 MHz, CDCl3) δ 8.33 – 8.26 (m, 1H), 7.62 – 7.23 (m, 4H), 7.08 – 6.81 (m, 7H), 6.64 (d, J = 8.7 Hz, 1H), 6.40 (dd, J =
24.5, 8.7 Hz, 2H), 3.57 (s, 3H), 1.33 (s, 6H), 0.92 (s, 4H). 13C{1H}NMR (100 MHz, CDCl3) δ 161.8, 159.5, 141.3, 136.7, 136.3, 133.6,
133.0, 130.3, 130.1, 129.0, 128.8, 128.7, 128.5, 128.4, 128.4, 127.4, 127.1, 113.1, 112.4, 55.3, 55.2, 52.3, 51.9, 28.5, 28.0. IR (ATR):  =
3352, 2967, 1659, 1532, 1505, 1308, 1290, 1248, 1221, 1147, 1087, 735, 686, 542 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for
C26H28NO4SSe 530.0889; Found 530.0871.
methyl 4-(3-(tert-butylamino)-3-oxo-1-(phenylselanyl)-2-(phenylsulfonyl)prop-1-en-1-yl)benzoate (3ia) Yield =88.0% (97.9 mg, 67 : 33).
White solid. 1H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 7.4 Hz, 1H), 7.73 – 7.51 (m, 5H), 7.41 (t, J = 7.7 Hz, 1H), 7.20 (s, 1H), 7.13 – 6.84
(m, 7H), 3.84 (s, 3H), 1.42 (s, 6H), 0.95 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 166.4, 161.3, 140.8, 139.7, 137.0, 136.6, 133.9, 133.4,
129.1, 129.0, 128.9, 128.8, 128.7, 128.5, 128.3, 128.1, 127.4, 52.4, 52.1, 28.5, 27.8. IR (ATR):  = 3354, 2968, 1722, 1657, 1532, 1447,
1310, 1273, 1218, 1148, 1087, 741, 685, 566 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C27H27NO5SSeNa 580.0668; found 580.0634.
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N-(tert-butyl)-3-(phenylselanyl)-2-(phenylsulfonyl)-3-(pyridin-3-yl)acrylamide (3ja) Yield = 71.1% (71.0 mg, 67 : 33). White solid. 1H
NMR (400 MHz, CDCl3) ) δ 8.32 (d, J = 7.5 Hz, 3H), 7.72 (t, J = 7.4 Hz, 1H), 7.62 (t, J = 7.6 Hz, 2H), 7.24 (s, 1H), 7.13 – 6.84 (m, 7H),
5.64 (s, 1H), 1.00 (s, 9H). 13C{1H}NMR (100 MHz, CDCl3) δ 161.2, 140.0, 138.5, 136.9, 135.7, 134.1, 129.1, 129.1, 129.0, 128.8, 127.5,
52.2, 28.0. IR (ATR): = 3229, 2988, 1666, 1544, 1291, 1220, 1145, 1083, 823, 743, 728, 690, 597, 549, 469 cm-1; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd. for C24H25N2O3SSe 501.0747; Found 501.0743.
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3-(phenylselanyl)-4-(phenylsulfonyl)but-3-en-1-yl 4-methylbenzenesulfonate (3ka) Yield = 56.9% (59.3 mg, E/Z >99% ). Yellow oil. 1H
NMR (400 MHz, CDCl3). δ 7.78 (dd, J = 15.0, 7.8 Hz, 4H), 7.60 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 7.42 (t, J = 8.6 Hz, 3H), 7.35
(d, J = 7.6 Hz, 4H), 5.91 (s, 1H), 4.27 (t, J = 6.7 Hz, 2H), 3.26 (t, J = 6.7 Hz, 2H), 2.45 (s, 3H).13C{1H}NMR (100 MHz, CDCl3) δ 154.2,
145.0, 141.4, 136.5, 133.4, 132.7, 130.3, 130.2, 129.9, 129.4, 128.1, 127.0, 126.1, 125.6, 68.6, 32.4, 21.7. IR (ATR):  = 3058, 2924, 1596,
1359, 1306, 1173, 1144, 1082, 973, 894, 741, 686, 658, 551, 473 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C23H22O5S2SeNa
544.9967; Found 544.9970.
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3-(1-(phenylselanyl)-2-(phenylsulfonyl)vinyl)pyridine (3la) Yield = 88.5% (70.9 mg, E/Z >99%). White solid. 1H NMR (400 MHz,
CDCl3) δ 8.54 (d, J = 6.4 Hz, 1H), 8.34 (d, J = 1.7 Hz, 1H), 7.57 (dd, J = 7.2, 1.5 Hz, 2H), 7.55 – 7.49 (m, 2H), 7.48 – 7.42 (m, 3H), 7.40 –
7.35 (m, 4H), 7.22 (dd, J = 7.8, 4.9 Hz, 1H), 6.29 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 153.7, 150.2, 148.2, 141.5, 136.6, 136.1,
133.2, 131.1, 130.4, 130.3, 129.0, 127.3, 127.2, 126.2, 122.7. IR (ATR):  = 3052, 2924, 1719, 1571, 1445, 1320, 1233, 1147, 1083, 936,
741, 684, 567, 532 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C19H16NO2SSe 402.0062; Found 402.0066.
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3-(1-(phenylselanyl)-2-(phenylsulfonyl)vinyl)thiophene (3ma) Yield = 70.9% (57.5 mg, E/Z >99%). White solid. H NMR (400 MHz,
CDCl3) δ 7.58 – 7.55 (m, 2H), 7.48 – 7.40 (m, 5H), 7.38 (dd, J = 3.4, 1.5 Hz, 2H), 7.34 – 7.30 (m, 2H), 7.18 (dd, J = 5.0, 3.0 Hz, 1H), 6.97
(dd, J = 5.0, 1.1 Hz, 1H), 6.21 (s, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 152.0, 141.6, 136.5, 134.3, 132.8, 130.3, 130.2, 128.7, 128.3,
127.3, 127.2, 126.9, 126.2, 125.4. IR (ATR):  = 2361, 1571, 1445, 1304, 1262, 1145, 1123, 1079, 848, 811, 740, 684, 550 cm-1; HRMS
(ESI-TOF) m/z: [M+Na] + Calcd. for C18H14O2S2SeNa 428.9493; Found 428.9469.
phenyl(1-phenyl-2-(phenylsulfonyl)vinyl)selane (3na) Yield = 89.1% (71.1 mg, 75: 25). White solid. 1H NMR (400 MHz, CDCl3) δ 7.59
(s, 2H), 7.41 (dq, J = 14.7, 6.7 Hz, 5H), 7.31 – 7.23 (m, 4H), 7.19 – 7.16 (m, 1H), 7.09 – 7.00 (m, 2H), 6.95 (t, J = 7.5 Hz, 1H), 6.17 (s, 1H).
13C{1H}NMR (100 MHz, CDCl3) δ 157.9, 141.7, 136.6, 135.8, 134.5, 133.6, 132.7, 130.3, 130.2, 129.4, 129.1, 128.7, 128.7, 128.6, 128.5,
127.9, 127.8, 127.6, 127.4, 126.8, 125.6. IR (ATR):  = 3050, 2958, 2923, 2853, 1574, 1443, 1317, 1142, 1081, 874, 794, 740, 688, 562,
530 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C20H17O2SSe 401.0109; Found 401.0113.
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1,5-diphenyl-1-(phenylselanyl)-2-(phenylsulfonyl)pent-1-en-3-one (3oa) Yield = 60.2% (640.0 mg, 81: 19). White solid. H NMR (400
MHz, CDCl3) δ 7.58 (d, J = 6.8 Hz, 2H), 7.44 – 7.24 (m, 11H), 7.19 (d, J = 7.0 Hz, 2H), 7.10 (d, J = 8.1 Hz, 3H), 7.05 – 6.93 (m, 1H), 6.16
(s, 1H), 2.47 (s, 1H), 2.36 (s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 157.2, 143.6, 138.9, 136.7, 135.9, 134.7, 130.3, 130.2, 129.4, 129.3,
128.6, 128.6, 127.9, 127.9, 127.5, 126.9, 125.9, 21.6. IR (ATR):  = 1606, 1574, 1438, 1318, 1274, 1139, 1081, 1022, 875, 801, 778, 741,
690, 649 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C29H25O3SSe 533.0685; Found 533.0690.
(1,2-diphenyl-2-(phenylsulfonyl)vinyl)(phenyl)selane (3pa) Yield =68.7 % (65.3 mg, 50: 50). White solid.1H NMR (400 MHz, CDCl3) δ
7.45 – 7.35 (m, 5H), 7.32 – 7.16 (m, 2H), 7.08 – 6.98 (m, 4H), 6.95 – 6.88 (m, 3H), 6.84 – 6.59 (m, 1H). 13C{1H}NMR(100 MHz, CDCl3) δ
141.0, 137.3, 137.2, 135.2, 132.8, 131.1, 129.5, 128.9, 128.9, 128.8, 128.8, 128.7, 128.5, 128.4, 128.3, 128.3, 127.7, 127.7, 127.5, 127.1. IR
(ATR):  = 3050, 2923, 1721, 1574, 1475, 1438, 1317, 1275, 1142, 1081, 874, 794, 740, 680, 587, 562, 530 cm-1; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd. for C26H21O2SSe 477.0427; Found 477.0452.
phenyl(1-phenyl-2,2-bis(phenylsulfonyl)vinyl)selane (3qa) Yield =22.3 % (24.0 mg, 67: 33). White solid. 1H NMR (400 MHz, CDCl3) δ
8.33 (d, J = 7.4 Hz, 2H), 7.73 (t, J = 7.4 Hz, 1H), 7.65 (t, J = 7.6 Hz, 2H), 7.46 (dd, J = 12.1, 7.5 Hz, 3H), 7.31 – 7.25 (m, 2H), 7.10 (t, J =
7.3 Hz, 1H), 7.00 (d, J = 7.0 Hz, 2H), 6.95 – 6.86 (m, 3H), 6.79 (t, J = 7.5 Hz, 2H), 6.48 (d, J = 7.3 Hz, 2H). 13C{1H}NMR(100 MHz, CDCl3)
) δ 176.1, 141.8, 141.5, 137.5, 134.2, 134.0, 133.2, 129.2, 129.0, 128.6, 128.5, 128.5, 128.1, 128.1, 128.0, 126.7. IR (ATR):  = 2359, 1502,
1469, 1442, 1313, 1150, 1080, 970, 823, 785, 744, 690, 550 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C26H21O4S2Se 541.0041; Found
541.0052.
diethyl 2-(phenylselanyl)-3-(phenylsulfonyl)fumarate (3ra) Yield = 36.0% (33.7 mg, 75: 25). White solid.1H NMR (400 MHz, CDCl3) δ
8.04 – 7.80 (m, 3H), 7.69 – 7.35 (m, 9H), 4.23 (q, J = 7.1 Hz, 2H), 3.60 (q, J = 7.1 Hz, 2H), 1.21 (t, J = 7.1 Hz, 3H), 1.07 (t, J = 7.2 Hz, 3H).
13C{1H}NMR(100 MHz, CDCl3) δ 166.2, 162.7, 162.6, 140.6, 138.0, 136.5, 133.5, 131.6, 130.6, 129.8, 129.0, 128.7, 128.7, 127.3, 62.7,
62.4, 13.9, 13.6. IR (ATR):  = 2975, 1740, 1714, 1685, 1526, 1476, 1443, 1325, 1308, 1260, 1204, 1151, 1087, 1062, 1049, 1023, 1006,
803, 748, 701, 684,622 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C20H20O6SSeNa 491.0038; Found 491.0037.
ethyl 3-((4-bromophenyl)selanyl)-3-phenyl-2-(phenylsulfonyl)acrylate (3ab) Yield = 69.8% (76.8 mg, 62: 38). White solid. 1H NMR (400
MHz, CDCl3) δ 8.31 (d, J = 7.4 Hz, 1H), 7.62 (dd, J = 11.6, 7.7 Hz, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 7.8 Hz, 1H), 7.11 – 6.76 (m,
9H), 4.38 (q, J = 7.2 Hz, 1H), 3.85 (q, J = 7.1 Hz, 1H), 1.36 (t, J = 7.1 Hz, 2H), 0.74 (t, J = 7.1 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) )
δ 163.5, 141.5, 138.4, 138.1, 134.4, 134.1, 133.1, 131.8, 131.8, 129.0, 128.7, 128.7, 128.6, 128.4, 128.2, 127.8, 127.3, 126.7, 124.0, 62.9,
62.1, 14.1, 13.3. IR (ATR):  = 1714, 1682, 1564, 1524, 1466, 1443, 1380, 1308, 1253, 1204, 1151, 1087, 1048, 1006, 803, 749, 702, 683,
622 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ calcd. for C25H25BrNO3SSe 577.9899; Found 577.9888.
ethyl 2-((4-chlorophenyl)sulfonyl)-3-phenyl-3-(phenylselanyl)acrylate (3ac) Yield = 79.9% (80.9 mg, 67: 33). White solid. 1H NMR (400
MHz, CDCl3) δ 8.28 (d, J = 8.7 Hz, 1H), 7.60 (d, J = 8.7 Hz, 1H), 7.50 (d, J = 8.7 Hz, 1H), 7.30 (d, J = 8.7 Hz, 1H), 7.13 – 6.92 (m, 9H),
6.87 – 6.83 (m, 1H), 6.75 (d, J = 6.8 Hz, 1H), 4.42 (q, J = 7.1 Hz, 1H), 3.84 (q, J = 7.1 Hz, 1H), 1.41 (t, J = 7.1 Hz, 2H), 0.73 (t, J = 7.1 Hz,
1H). 13C{1H}NMR (100 MHz, CDCl3) δ 165.9, 140.2, 139.7, 137.0, 136.7, 130.1, 129.7, 129.3, 129.1, 128.8, 128.8, 128.7, 128.7, 128.7,
128.6, 128.5, 128.2, 127.6, 127.6, 127.2, 62.9, 62.1, 14.2, 13.3. IR (ATR):  = 2987, 2361, 1712, 1576, 1475, 1329, 1248, 1150, 1085, 1040,
756, 689, 581, 552, 467 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C23H19ClO4SSeNa 528.9750; Found 528.9736.
ethyl 2-((4-fluorophenyl)sulfonyl)-3-phenyl-3-(phenylselanyl)acrylate (3ad) Yield = 80.2% (78.5 mg, 70: 30). White solid. 1H NMR (400
MHz, CDCl3) δ 8.39 – 8.33 (m, 1H), 7.61 – 7.54 (m, 1H), 7.29 (t, J = 8.6 Hz, 1H), 7.13 – 6.91 (m, 9H), 6.87 – 6.83 (m, 1H), 6.78 – 6.74 (m,
1H), 4.42 (q, J = 7.1 Hz, 1H), 3.84 (q, J = 7.1 Hz, 1H), 1.41 (t, J = 7.1 Hz, 2H), 0.73 (t, J = 7.1 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3)
δ 165.4(d, JF-C = 254.2 Hz), 165.2, 163.5, 137.0(d, JF-C = 3.1 Hz), 136.8, 134.3, 131.6(d, JF-C = 9.5 Hz), 131.(d, JF-C = 9.6 Hz), 129.1, 128.9,
128.7, 128.7, 128.6, 128.5, 128.2, 127.7, 127.6, 127.2, 116.3(d, J F-C = 22.6 Hz), 115.8 (d, J F-C = 22.4 Hz) 62.9, 62.1, 14.2, 13.4. IR (ATR):
 = 3354, 2977, 2363, 1684, 1587, 1525, 1490, 1319, 1261, 1224, 1145, 1085, 844, 818, 739, 691, 578 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+
Calcd. for C23H19FO4SSeNa 513.0046; Found 513.0038.
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ethyl 2-(methylsulfonyl)-3-phenyl-3-(phenylselanyl)acrylate (3ae) Yield = 65.8% (53.9 mg, 62: 38). White solid. H NMR (300 MHz,
CDCl3) δ 7.19 (d, J = 6.9 Hz, 2H), 7.11 (t, J = 7.4 Hz, 1H), 7.04 – 6.96 (m, 5H), 6.95 – 6.90 (m, 2H), 3.87 (q, J = 7.1 Hz, 2H), 3.39 (s, 3H),
0.76 (t, J = 7.1 Hz, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 163.5, 162.3, 137.0, 136.3, 131.5, 128.9, 128.7, 128.6, 128.0, 127.8, 127.6, 62.1,
42.0, 13.4. IR (ATR):  = 2984, 2357, 1706, 1535, 1438, 1315, 1237, 1201, 1143, 1043, 960, 765, 744, 688, 533, 473 cm-1; HRMS (ESI-
TOF) m/z: [M+H]+ Calcd. for C18H19O4SSe 411.0164; Found 411.0162.
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ethyl 3-phenyl-3-(phenylselanyl)-2-tosylacrylate (3af) Yield = 81.8% (79.5 mg, 62: 39). White solid. 1H NMR (400 MHz, CDCl3) δ 8.20
(d, J = 8.3 Hz, 1H), 7.44 (dd, J = 25.0, 8.2 Hz, 2H), 7.17 – 6.74 (m, 11H), 4.39 (q, J = 7.1 Hz, 1H), 3.84 (q, J = 7.1 Hz, 1H), 2.49 (s, 1H),
2.37 (s, 2H), 1.39 (t, J = 7.1 Hz, 2H), 0.74 (t, J = 7.1 Hz, 1H). 13C{1H}NMR (100 MHz, CDCl3) δ 163.6, 144.0, 138.7, 136.9, 136.7, 134.4,
129.5, 129.1, 128.9, 128.6, 128.6, 128.5, 128.4, 128.3, 128.3, 128.2, 127.8, 127.5, 127.0, 62.7, 61.9, 21.8, 21.6, 14.1, 13.3. IR (ATR):  =
2339, 1715, 1441, 1324, 1245, 1148, 1085, 748, 690, 553 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C24H23O4SSe 487.0477; Found
487.0460.
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ethyl 3-(sec-butylselanyl)-3-phenyl-2-(phenylsulfonyl)acrylate (3ag) Yield = 86.8% (78.4 mg, 90: 10). Yellow oil. H NMR (400 MHz,
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CDCl3) δ 8.29 (d, J = 7.3 Hz, 2H), 7.61 (dt, J = 38.7, 7.4 Hz, 3H), 7.35 – 7.27 (m, 3H), 7.26 – 7.17 (m, 2H), 3.89 (q, J = 7.1 Hz, 2H), 2.24
(h, J = 6.9 Hz, 1H), 1.58 (s, 1H), 1.40 – 1.22 (m, 2H), 1.17 – 0.98 (m, 3H), 0.81 (t, J = 7.1 Hz, 2H), 0.62 (t, J = 7.3 Hz, 3H). 13C{1H}NMR
(100 MHz, CDCl3) δ 159.9, 140.6, 137.5, 133.6, 129.4, 128.6, 128.5, 128.2, 127.8, 61.9, 42.7, 30.4, 21.4, 13.3, 11.8. IR (ATR):  = 2962,
1719, 1542, 1445, 1320, 1238, 1204, 1148, 1085, 1041, 998, 857, 743, 685, 547 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for
C21H25O4SSe 453.0634; Found 453.0635.
ethyl 3-((cyclopropylmethyl)selanyl)-3-phenyl-2-(phenylsulfonyl)acrylate (3ah) Yield =76.1% (68.5 mg, 75: 25). White oil. 1H NMR (400
MHz, CDCl3) δ 7.74 – 7.28 (m, 8H), 7.19 – 7.03 (m, 2H), 4.39 (q, J = 7.1 Hz, 2H), 2.03 (dd, J = 13.6, 7.5 Hz, 2H), 1.38 (t, J = 7.1 Hz, 2H),
0.86 – 0.45 (m, 4H), 0.04 (p, J = 5.8, 5.3 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 164.4, 163.6, 141.8, 135.4, 133.7, 132.9, 131.8, 129.3,
129.0, 128.7, 128.5, 128.5, 128.4, 128.0, 128.0, 127.8, 127.5, 62.5, 61.9, 34.8, 14.0, 13.4, 9.8, 6.9, 6.8. IR (ATR):  = 3333, 2975, 2361,
1708, 1529, 1313, 1246, 1147, 1084, 1044, 751, 691, 596, 553cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C21H22O4SSeNa 473.0297;
Found 473.0283.
3-((4-bromophenyl)selanyl)-N-(tert-butyl)-3-phenyl-2-(phenylsulfonyl)acrylamide (3db) Yield =73.2% ( 84.5 mg, 81: 19). White solid. 1H
NMR (400 MHz, CDCl3) δ 7.63 – 7.48 (m, 3H), 7.38 (t, J = 7.8 Hz, 2H), 7.08 – 6.93 (m, 7H), 6.75 (d, J = 6.8 Hz, 2H), 1.41 (s, 7H), 0.94 (s,
2H). 13C{1H}NMR (100 MHz, CDCl3) δ 161.7, 141.1, 138.5, 138.1, 134.9, 133.3, 131.8, 131.5, 128.94, 128.9, 128.5, 128.4, 128.3, 128.1,
128.0, 127.4, 127.1, 123.6, 52.5, 28.6, 27.9. IR (ATR):  = 1714, 1682, 1524, 1477, 1443, 1380, 1308, 1253, 1204, 1151, 1087, 1048, 1006,
803, 749, 702, 683, 622 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C25H25BrNO3SSe 577.9899; Found 577.9888.
N-(tert-butyl)-2-((4-chlorophenyl)sulfonyl)-3-phenyl-3-(phenylselanyl)acrylamide (3dc) Yield = 78.2% (83.4 mg, 59: 41). White solid. 1H
NMR (400 MHz, CDCl3) δ 8.32 (d, J = 8.7 Hz, 1H), 7.58 (d, J = 8.7 Hz, 1H), 7.48 (d, J = 8.7 Hz, 1H), 7.31 (d, J = 8.7 Hz, 1H), 7.12 – 6.90
(m, 10H), 6.72 (d, J = 8.2 Hz, 1H), 1.46 (s, 5H), 0.94 (s, 4H). 13C{1H}NMR(100 MHz, CDCl3) δ 164.4, 161.6, 139.8, 139.7, 139.0, 137.0,
136.6, 134.5, 130.4, 129.1, 129.0, 129.0, 128.7, 128.7, 128.6, 128.6, 128.4, 128.4, 128.1, 127.8, 127.0, 52.6, 52.0, 28.6, 27.9. IR (ATR):  =
3335, 2361, 1661, 1525, 1314, 1146, 1084, 752, 744, 688, 555, 742 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C25H24ClNO3SSeNa
556.0223; Found 556.0193.
N-(tert-butyl)-2-((4-fluorophenyl)sulfonyl)-3-phenyl-3-(phenylselanyl)acrylamide (3dd) Yield = 87.5% (90.4 mg, 67: 33). White solid. 1H
NMR (400 MHz, CDCl3) δ 7.57 (dd, J = 8.9, 5.1 Hz, 1H), 7.30 – 7.24 (m, 1H), 7.12 – 6.90 (m, 11H), 6.74 – 6.72 (m, 1H), 1.46 (s, 6H), 0.94
(s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ164.9 (d, J F-C = 6.5 Hz), 164.0 (d, J F-C = 6.8 Hz), 161.9, 161.8, 137.4 (d, J F-C = 3.0 Hz), 137.1,
136.7, 134.7, 132.6 (d, J F-C = 3.6 Hz), 131.9 (d, J F-C = 9.4 Hz), 130.5 (d, J F-C = 9.9 Hz), 128.8, 128.7, 128.7, 128.6, 128.5, 128.4, 128.2,
127.9, 127.0, 116.1(d, J F-C = 22.4 Hz), 116.1(d, J F-C = 22.8 Hz), 115.9, 52.7, 52.0, 28.7, 27.9. IR (ATR):  = 3352, 2967, 1656, 1531, 1493,
1316, 1292, 1218, 1144, 1086, 841, 732, 691, 551, 507 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C25H25FNO3SSe 518.0669; Found
518.0669.
N-(tert-butyl)-2-(methylsulfonyl)-3-phenyl-3-(phenylselanyl)acrylamide (3de) Yield =74.7% (65.2 mg, 69: 31). White solid. 1H NMR (400
MHz, CDCl3) δ 7.15 (ddd, J = 21.1, 15.2, 7.2 Hz, 3H), 7.05 – 6.96 (m, 6H), 6.93 – 6.91 (m, 1H), 3.40 (s, 1H), 2.89 (s, 2H), 1.52 (s, 6H), 0.94
(s, 3H). 13C{1H}NMR (100 MHz, CDCl3) δ 162.2, 137.1, 137.0, 134.8, 128.8, 128.7, 128.6, 128.5, 128.3, 128.2, 128.0, 127.2, 52.7, 52.0,
44.2, 42.3, 28.7, 27.9. IR (ATR):  = 3333, 2975, 2364, 1659, 1532, 1307, 1140, 746,521 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for
C20H23NO3SSeNa 460.0457; Found 460.0456.
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N-(tert-butyl)-3-phenyl-3-(phenylselanyl)-2-tosylacrylamide (3df) Yield =95.9 % ( 98.3 mg, 60: 40). White solid. H NMR (400 MHz,
CDCl3) δ 8.23 (d, J = 8.2 Hz, 1H), 7.43 (dd, J = 31.5, 8.2 Hz, 2H), 7.17 – 6.75 (m, 12H), 2.47 (s, 1H), 2.36 (s, 2H), 1.43 (s, 5H), 0.93 (s,
4H). 13C{1H}NMR (100 MHz, CDCl3) δ 161.8, 161.8, 144.1, 138.2, 137.0, 136.7, 134.9, 129.4, 129.4, 128.8, 128.5, 128.5, 128.4, 128.4,
128.3, 127.9, 127.6, 127.6, 126.8, 52.3, 51.8, 28.5, 27.8, 21.8, 21.6. IR (ATR):  = 3332, 2974, 2358, 1660, 1526, 1304, 1218, 1143, 1086,
689, 554 cm-1; HRMS (ESI-TOF) m/z: [M+Na]+ Calcd. for C26H27NO3SSeNa 536.0769; Found 536.0783.
N-(tert-butyl)-3-(sec-butylselanyl)-3-phenyl-2-(phenylsulfonyl)acrylamide (3dg) Yield =44.9 % (43.0 mg, 81: 19). White solid. . 1H NMR
(400 MHz, CDCl3) δ 7.62 – 7.59 (m, 2H), 7.56 – 7.53 (m, 3H), 7.36 (dt, J = 15.6, 7.9 Hz, 5H), 5.95 (s, 1H), 1.56 (s, 3H), 1.49 (d, J = 2.6 Hz,
9H), 1.43 – 0.83 (m, 6H). 13C{1H}NMR (100 MHz, CDCl3) δ 159.3, 149.0, 147.3, 139.4, 136.7, 134.5, 134.1, 129.7, 129.6, 129.0, 128.9,
128.8, 128.8, 128.4, 128.0, 127.9, 125.4, 53.4, 28.5, 28.4. IR (ATR):  = 3368, 2975, 2361, 1672, 1526, 1446, 1322, 1152, 1081, 809, 686,
548 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C23H30NO3SSe 480.1107; Found 480.1118.
N-(tert-butyl)-3-((cyclopropylmethyl)selanyl)-3-phenyl-2-(phenylsulfonyl)acrylamide (3dh) Yield =53.8% (51.3 mg, 67: 33). White solid.
1H NMR (400 MHz, CDCl3) δ 8.39 (d, J = 7.4 Hz, 1H), 7.72 – 7.55 (m, 3H), 7.49 – 7.35 (m, 5H), 7.29 (d, J = 5.6 Hz, 1H), 7.12 (d, J = 9.3
Hz, 1H), 6.85 (s, 1H), 2.02 (dd, J = 25.3, 7.4 Hz, 2H), 1.46 (s, 6H), 1.05 (s, 3H), 0.72 (dt, J = 38.1, 7.7 Hz, 1H), 0.50 (dd, J = 34.9, 6.9 Hz,
2H), 0.04 (dd, J = 27.0, 4.8 Hz, 2H). 13C{1H}NMR (100 MHz, CDCl3) δ 161.8, 141.4, 135.9, 133.5, 133.1, 129.2, 128.8, 128.8, 128.7, 128.6,
128.6, 127.9, 127.8, 127.8, 127.5, 52.3, 51.9, 34.4, 28.5, 28.0, 10.3, 9.7, 6.8, 6.8. IR (ATR):  = 3354, 2358, 1656, 1529, 1309, 1222, 1150,
1088, 736, 685, 551 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C23H28NO3SSe 478.0950; Found 478.0944.
(2-(p-tolyl)ethene-1,1-diyl)dibenzene (5) Yield =53.8% (51.3 mg). White solid. 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.2 Hz, 2H), 7.39
– 7.27 (m, 6H), 7.20 (d, J = 7.3 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H), 7.10 (d, J = 7.1 Hz, 2H), 6.99 (s, 1H), 2.37 (s, 3H). 13C{1H}NMR (100
MHz, CDCl3) δ 154.8, 143.8, 139.3, 138.7, 135.6, 130.3, 129.8, 129.4, 129.0, 128.9, 128.6, 128.3, 127.9, 127.8, 21.6. IR (ATR):  = 3037,
2358, 1591, 1443, 1299, 1134, 1084, 804, 759, 694, 579, 536 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd. for C21H19O2S 335.1101; Found
335.1089.
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ASSOCIATED CONTENT
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Supporting Information Available.
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The copies of 1H and 13C NMR spectra of the products and crystallographic data of 3aa, 3da.
This material is available free of charge via the Internet at http://pubs.acs.org.
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The syntheses and characterization of compounds 3aa, 3ah, 3da, and 3df were repeated and checked by
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Jing-Hao Li in our group.
ACKNOWLEDGMENT
We gratefully acknowledge the National Natural Science Foundation of China (21772137, 21542015 and
21672157), PAPD, the project of scientific and technologic infrastructure of Suzhou (SZS201708), the
Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education
Institutions (No.16KJA150002), and Soochow University for financial support.
REFERENCES
(1) (a) Paulmier, C. Selenium Reagents and Intermediates in Organic Synthesis, Pergamon, Oxford, U.K., 1986; (b)
Patai, S.; Rappoport, Z. The Chemistry of Organic Selenium and Tellurium Compounds, Wiley, New York, 1986;
(c) Liotta, D. Organoselenium Chemistry, Wiley, New York, 1987; (d) Krief, A.; Hevesi, L. Organoselenium
Chemistry I, Springer, Berlin, 1988; (e) Back, T. G. Organoselenium Chemistry: A Pratical Approach, Oxford
University Press, Oxford, U.K., 1999; (f) Liotta, D. New organoselenium methodology. Acc. Chem. Res. 1984, 17,
28-34; (g) Wirth, T. Organoselenium Chemistry–Modern Developments in Organic Synthesis, Topics in Current
Chemistry 208, SpringVerlag, Heidelberg, Germany, 2000; (h) Mugesh, G.; Singh, H. B. Heteroatom-Directed
Aromatic Lithiation:ꢀ A Versatile Route to the Synthesis of Organochalcogen (Se, Te) Compounds. Acc. Chem. Res.
2002, 35, 226-236.
(2) For selected examples, see: (a) Kuniyasu, H.; Ogawa, A.; Sato, K.-L.; Ryu, I.; Sonoda, N. The first example of
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