Cesium Salt-Catalyzed Addition of Diphenyl Dichalcogenides to Alkynes: Selective Synthesis of Bis- and Mono(phenylchalcogeno)alkenes

Article abstract of DOI:10.1246/bcsj.82.1170

A cesium salt has a unique catalytic ability for the reaction of alkynes with diphenyl dichalcogenides. When the diphenyl dichalcogenides, such as the disulfide, diselenide, or ditelluride, were allowed to react with alkynes in the presence of a catalytic

Full text of DOI:10.1246/bcsj.82.1170

1170 Bull. Chem. Soc. Jpn. Vol. 82, No. 9, 1170–1174 (2009)
© 2009 The Chemical Society of Japan
Cesium Salt-Catalyzed Addition of Diphenyl Dichalcogenides to Alkynes:
Selective Synthesis of Bis- and Mono(phenylchalcogeno)alkenes
Yutaka Nishiyama,* Haruko Ohnishi, and Yuya Koguma
Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680
Received June 6, 2008; E-mail: nishiya@ipcku.kansai-u.ac.jp
A cesium salt has a unique catalytic ability for the reaction of alkynes with diphenyl dichalcogenides. When the
diphenyl dichalcogenides, such as the disulfide, diselenide, or ditelluride, were allowed to react with alkynes in the
presence of a catalytic amount of a cesium fluoride or carbonate, the bisphenylchalcogenolation of the alkynes efficiently
proceeded to give the corresponding vic-bis(phenylchalcogeno)alkenes in moderate to good yields with high selectivity.
When H2O was added to the reaction medium, monophenylchalcogenolation of the alkynes occurred giving the
mono(phenylchalcogeno)alkenes in moderate yields.
One direct synthetic method of vic-bis(phenylchalcogeno)-
alkenes involves the addition of diphenyl dichalcogenides,
such as the disulfide, diselenide, or ditelluride, to the carbon-
carbon triple bond of alkynes. It has already been reported that
the diphenyl dichalcogenides add to terminal alkynes in the
presence of a transition-metal catalyst1 or under irradiation of
near-UV light2 to produce vic-bis(phenylchalcogeno)alkenes in
moderate to good yields. As another method, Oshima et al.
recently showed that GaCl3 assisted the bisphenylthiolation of
alkynes with diphenyl disulfide.3 It was shown that reaction of
diphenyl dichalcogenides proceeds with propargylic alcohols
in the presence of butyllithium4 or with phenylacetylene in the
presence of alumina-supported sodium borohydride.5 We now
discovered the cesium-catalyzed bisphenylchalcogenolation of
alkynes with diphenyl dichalcogenides to give the correspond-
ing vic-bis(phenylchalcogeno)alkenes in moderate to good
yields with high selectivity. Furthermore, in the presence of
water, the monophenylchalcogenation of alkynes predominant-
ly occurrs to give mono(phenylchalcogeno)alkenes in moderate
yields (Scheme 1).6,7
smoothly proceeded to give the ethyl 2,3-bis(phenylseleno)-
acrylate (2a) in 74% yield (E/Z = 22/78) along with the
formation of the ethyl 3-(phenylseleno)acrylate (16%) and
ethyl 3-(phenylseleno)propiolate (3%) as by-products (Entry 3
in Table 1).6 In the absence of the cesium salt, 2a was not
formed, and the starting materials were recovered (Entry 1). By
increasing the amount of the diselenide, the yield of 2a was
improved (Entry 4). Similarly, in the presence of a catalytic
amount of cesium carbonate, the bisphenylselenolation of 1a
occurred to give 2a in 82% yield (Entry 8). In contrast, in the
case of other cesium salts, such as cesium chloride, bromide,
Table 1. Reaction of Ethyl Propiolate with Diphenyl
Diselenidea)
COOC2H5
1a
+
PhSeSePh
catalyst
SePh
COOC2H5
PhSe
2a
Entry
Catalyst
Yield/%b)
1
2c)
3d)
4f)
5
6
7
8
9
None
CsF
CsF
trace
3
Results and Discussion
When diphenyl diselenide was allowed to react with ethyl
propiolate (1a) in the presence of a catalytic amount of
cesium fluoride (8 mol %) in THF solvent at 67 °C for 5 h,
the bisphenylselenolation of the carbon-carbon triple bond
74 (22/78)e)
CsF
89
9
5
CsCl
CsBr
CsI
Cs2CO3
KF
9
cat.Cs salt
82
49
40
22
+
R
(PhY)2
YPh
10
11
NaF
LiF
PhY
H2O
R
a) Reaction conditions: PhSeSePh (0.30 mmol), 1a (0.25
mmol), catalyst (0.02 mmol), and THF (2.5 mL) at 67 °C for
5 h. b) GC yield based on 1a. c) Reaction was carried out at
25 °C. d) Ethyl 3-(phenylseleno)acrylate (16%) and ethyl 3-
(phenylseleno)propiolate (3%) were formed. e) The number
in parenthesis shows the ratios of the E and Z isomers.
f) PhSeSePh (3.00 mmol) was used.
+
+
R
(PhY)2
cat.Cs salt
PhY
R
Scheme 1.
Published on the web September 9, 2009; doi:10.1246/bcsj.82.1170

Y. Nishiyama et al.
Table 2. Cesium Salt-Catalyzed Reaction of Alkynes with Diselenidesa)
Bull. Chem. Soc. Jpn. Vol. 82, No. 9 (2009) 1171
Yield/%b)
(E/Z)
Entry
1
Diselenide
Alkyne
Product
SePh
74
(22/78)
(PhSe)2
COOC2H5 1a
2a
2b
2c
2d
2e
PhSe
PhSe
PhSe
COOC2H5
SePh
72
(22/78)
2
(PhSe)2
(PhSe)2
(PhSe)2
COOCH3 1b
COOCH3
SePh
51
(35/65)
3
COCH3
Ph
1c
COCH3
SePh
68d)
(71/29)
4c)
5
1d
PhSe
Ph
SeCON(C2H5)2
50
(25/75)
(C2H5)2N
C
O
Se
COOCH3 1b
(C2H5)2NOCSe
2
COOCH3
a) Reaction conditions: diselenide (0.30 mmol), alkyne (0.25 mmol), CsF (0.02 mmol), and THF (2.5 mL) at 67 °C for
5 h. b) GC yield based on alkyne. c) Reacton conditions: PhSeSePh (0.30 mmol), phenylacetylene (0.60 mmol),
Cs2CO3 (0.02 mmol), and dimethylacetamide (DMA) (2.5 mL) at 125 °C for 5 h. d) GC yield based on diselenide.
Table 3. Cesium Carbonate-Catalyzed Reaction of Alkynes
with Diphenyl Disulfidea)
COOC2H5
(0.60 mmol)
+
PhTeTePh
(0.30 mmol)
cat.Cs2CO3
SPh
PhSSPh
+
R
cat.Cs2CO3
(0.02 mmol)
TePh
PhS
R
1
3
PhTe
COOC2H5
60 % (E/Z = 5/95)
Scheme 2.
THF (2.5 mL)
67 °C, 5 h
Entry
R
Yield/%b) (E/Z)
1
2
3c)
COOC2H5 (1a)
COOCH3 (1b)
Ph (1d)
3a
73 (23/77)
73 (25/75)
89d) (3/97)
3b
3c
a) Reaction conditions: PhSSPh (1.0 mmol), alkyne (1.0
mmol), Cs2CO3 (0.2 mmol), and DMA (2.5 mL) at 67 °C for
5 h. b) GC yield based on alkyne. c) Phenylacetylene (2.0
mmol) was used. At 125 °C. d) GC yield based on phenyl-
acetylene.
PhSe
R
4
Figure 1.
and iodide, the bisphenylselenolation hardly proceeded (Entries
5-7). In the presence of another alkaline metal fluoride, the
yields of 2a slightly decreased (Entries 9-11).
bis(N,N-diethylcarbamoylseleno)acrylate was formed in 50%
yield (Entry 5).
Next, the cesium salt-catalyzed bisphenylthiolation of
alkynes with diphenyl disulfide was examined and these results
are shown in Table 3. Similarly, the addition of diphenyl
disulfide to the carbon-carbon triple bond of ethyl and methyl
propiolates occurred to give both the ethyl and methyl 2,3-
bis(phenylthio)acrylates in 73% yield (Entries 1 and 2). In the
case of the phenylacetylene, the bisphenylthiolation did not
proceed under the same reaction conditions as that of ethyl
propiolate; however, the bisphenylthiolation did occur by
raising the reaction temperature (Entry 3). Similarly, the
bisphenyltellurolation of ethyl propiolate with diphenyl ditel-
luride took place to afford the vic-bis(phenyltelluro)alkenes in
60% yield (Scheme 2).
To determine the scope and limitations of the cesium salt-
catalyzed bisphenylselenolation of alkynes with diphenyl
diselenide, the diphenyl diselenide was allowed to react with
various alkynes in the presence of a catalytic amount of cesium
fluoride (8 mol %) and these results are shown in Table 2. For
the reaction of the methyl and ethyl propiolates, and 3-
oxobutyne, which have an electron-withdrawing group adjacent
to the carbon-carbon triple bond, the bisphenylselenolation of
the carbon-carbon triple bond smoothly took place to give the
corresponding vic-bis(phenylseleno)alkenes in moderate yields
(Entries 1-3). In the case of phenylacetylene, the product yield
was low (19%) under the same reaction conditions as that of
ethyl propiolate, however the product yield was improved
using two equimolar amounts of phenylacetylene (0.60 mmol)
(Entry 4). When bis(N,N-diethylcarbamoyl) diselenide instead
of diphenyl diselenide was used as the diselenide, methyl 2,3-
Upon the cesium salt-catalyzed addition of the dichalco-
genides to terminal alkynes, the alkynyl phenyl selenide 4
(Figure 1) was observed as the by-product. The result
suggested that the acetylide was generated in situ by deproto-

1172 Bull. Chem. Soc. Jpn. Vol. 82, No. 9 (2009)
Cesium Salt-Catalyzed Addition
CsF (0.60 mmol)(CH3)3SiCl
H2O
Ph
+
+
(PhY)2
COOC2H5
(2.0 mmol)
(1.0 mmol)
(50.0 mmol)
THF (2.5 mL)
(0.60 mmol)
67 °C, 5 h
cat.Cs2CO3 (0.2 mmol)
PhY
(H3C)3Si
COOC2H5
Ph
DMA (2.5 mL)
125 °C, 5 h
10 %
Y = S (6a) 95 % (E/Z = 56/44)
Y = Se (6b) 40 % (E/Z = 61/39)
Scheme 3.
Scheme 5.
H
R
CsF
R
Cs
PhSeSePh
PhSe
R
4
R
H
R
PhSe
PhSe
SePh
2
R
PhSeSePh
PhSe
5
Scheme 4.
nation of the terminal alkynes. In fact, when ethyl propiolate
was treated with cesium fluoride and subsequently the reaction
mixture was quenched with chlorotrimethylsilane the reaction
gave ethyl 3-trimethylsilylpropiolate in 10% yield (Scheme 3).
We cannot explain the reaction pathway in detail, but a
plausible reaction pathway is shown in Scheme 4. The first step
of the reaction is the generation of the acetylide by deproto-
nation of the terminal alkynes with the cesium salt. The
acetylide is trapped with diselenide to form the alkynyl phenyl
selenide 4, and the phenyl selenolate.8 The phenyl selenolate
adds to the carbon-carbon triple bond to form the vinyl anion
5 and 5 is quenched with diphenyl diselenide giving the
corresponding bis(phenylseleno)alkenes 2 and regenerating the
phenyl selenolate. Another generation pathway of the phenyl
selenolate by the reaction of the diphenyl diselenide with the
cesium salt cannot be ruled out.9
Mono(phenylchalcogeno)alkenes are widely used as syn-
thetic intermediates in organic synthetic reactions10 and
as electrophotographic photoreceptors.11 There is increasing
interest in development of a method for the synthesis of
mono(phenylchalcogeno)alkenes.12 The addition of a thiol or
selenol or alkali metal salts of these compounds to the carbon-
carbon triple bond is one direct synthetic method for mono-
(phenylchalcogeno)alkenes; however, there are some disadvan-
tages to these methods: (i) handling of the thiol and selenol,
which are bad smelling and unstable compounds in air (ii) the
use of an excess amount of alkali metals, and (iii) the reaction
under nonaqueous conditions. From the proposed reaction
pathways including the formation of the vinyl anion 5, the
cesium-catalyzed reaction of alkynes with diphenyl dichalco-
genide in the presence of H2O was investigated to prepare
the mono(phenylchalcogeno)alkenes. When diphenyl disulfide
or diselenide was allowed to react with phenylacetylene
in the presence of a catalytic amount of cesium carbonate
(20 mol %) and an excess amount of water in DMA solvent at
125 °C for 5 h, the monophenylthiolation and monophenyl-
selenolation of the phenylacetylene smoothly proceeded to give
the corresponding mono(phenylchalcogeno)alkenes 6 in 95 and
40% yields (Scheme 5).
Conclusion
In summary, we discovered the unique catalytic ability
of cesium fluoride and carbonate for the reaction of alkynes
with diphenyl dichalcogenides. The bisphenylchalcogenolation
of the carbon-carbon triple bond with diphenyl dichalco-
genides, such as the disulfide, diselenide, or ditelluride in the
presence of a cesium fluoride or carbonate catalyst efficiently
proceeded to give the vic-bis(phenylchalcogeno)alkenes in
moderate to good yields. In addition, the mono(phenylchalco-
geno)alkenes were formed by the cesium salt-catalyzed
reaction of the alkynes with the diphenyl dichalcogenides and
water.

Y. Nishiyama et al.
Bull. Chem. Soc. Jpn. Vol. 82, No. 9 (2009) 1173
¤ 8.39 (s, 0.23H), 7.68-7.19 (m, 10H), 5.33 (s, 0.77H), 4.15 (q,
J = 8.1 Hz, 0.23 © 2H), 4.13 (qd, J = 8.1 and 1.6 Hz, 0.77 © 2H),
1.23 (t, J = 8.1 Hz, 0.77 © 3H), 1.14 (t, J = 8.1 Hz, 0.23 © 3H);
13C NMR (CDCl3, 100 MHz): ¤ 166.5, 164.2, 149.7, 146.7, 136.1,
133.0, 131.1, 129.6, 129.3, 129.1, 128.2, 115.5, 113.3, 60.3, 60.3,
14.3, 14.2; IR (KBr): 3059, 2980, 1690, 1534, 1171, 814, 748,
689 cm¹1; MS m/z 316 (M+); Anal. Calcd for C17H16O2S2: C,
64.53; H, 5.10; S, 20.27%. Found: C, 64.82; H, 4.98; S, 20.53%.
3b (a mixture of E/Z isomers) 1H NMR (CDCl3, 270 MHz): ¤
7.69-7.36 (m, 10H), 7.26 (s, 0.25H), 5.30 (s, 0.75H), 3.66 (s,
0.75 © 3H), 3.49 (s, 0.25 © 3H); 13C NMR (CDCl3, 100 MHz): ¤
165.6, 163.7, 136.9, 135.3, 131.3, 130.2, 130.1, 130.0, 129.8,
129.5, 129.0, 128.8, 128.7, 126.3, 107.7, 51.1; IR (KBr): 3058,
2947, 1697, 1534, 1303, 1171, 813, 749, 689 cm¹1; MS m/z 302
(M+); Anal. Calcd for C16H14O2S2: C, 63.55; H, 4.67; S, 21.21%.
Found: C, 63.49; H, 4.51; S, 21.56%.
Typical Procedure for Cesium Salt-Catalyzed Reaction of
Ethyl Propiolate with Diphenyl Ditelluride. A THF (2.5 mL)
solution of diphenyl ditelluride (123 mg, 0.30 mmol), ethyl
propiolate (59 mg, 0.60 mmol), and cesium carbonate (65 mg,
0.02 mmol) was stirred at 67 °C for 5 h under nitrogen atmosphere.
After the reaction was complete, aq HCl (5%) (20 mL) was added
to the reaction mixture and the resultant solution was extracted
with diisopropyl ether (20 mL © 3). The organic layer was dried
over MgSO4. The resulting mixture was filtered, and the filtrate
was concentrated. Purification of the residue by HPLC afforded the
corresponding vic-(bisphenyltelluro)alkenes. The product was
characterized by comparing its spectral date with those of authentic
sample 3c.1a
Experimental
General Procedures.
The 1H and 13C NMR spectra were
recorded on 400 and 100 MHz spectrometers using CDCl3 as
the solvent with tetramethylsilane as the internal standard. The
IR spectra were recorded on an FT-IR spectrometer. Gas
chromatography (GC) was carried out using a flame-ionizing
detector-equipped instrument and a capillary column (0.25 mm ©
1200 mm). The HPLC separation was performed using a recycl-
ing preparative HPLC equipped with GPC columns (20 mm ©
1200 mm).
Reagents. Diphenyl disulfide, the alkynes, the cesium salts,
and alkaline metal salts were purchased as high grade products,
and used without further purification. Diphenyl diselenide13 and
bis(N,N-diethylcarbamoyl) diselenide14 were synthesized as de-
scribed in the literature. The solvents were purified before use by
the usual methods.
General Procedure for Cesium Salt-Catalyzed Reaction of
Alkyne with Diphenyl Diselenide. A THF (2.5 mL) solution of
diselenide (0.30 mmol), alkyne (0.25 or 0.60 mmol), and cesium
fluoride (3 mg, 0.02 mmol) was stirred at 67 °C for 5 h under a
nitrogen atmosphere. After the reaction was complete, aq HCl
(5%) (20 mL) was added to the reaction mixture, and the resultant
solution was extracted with diisopropyl ether (20 mL © 3). The
organic layer was dried over MgSO4. The resulting mixture was
filtered, and the filtrate was then concentrated. Purification of the
residue by HPLC afforded the corresponding vic-bischalcogeno-
alkenes. The product was characterized by comparing its spectral
data with those of authentic samples 2a,2b 2b,1a and 2d.1c The
structures of the product were assigned by their H and 13C NMR,
General Procedure for Cesium Salt-Catalyzed Reaction of
1
IR, and mass spectra.
2c (a mixture of E/Z isomers) H NMR (CDCl3, 400 MHz): ¤
Phenylacetylene with Diphenyl Chalcogenide and Water.
A
1
DMA (2.5 mL) solution of diphenyl dichalcogenide (1.0 mmol),
phenylacetylene (2.0 mmol), H2O (50.0 mmol), and cesium car-
bonate (65 mg, 0.2 mmol) was stirred at 125 °C for 5 h under
a nitrogen atmosphere. After the reaction was complete, aq
HCl (5%) (20 mL) was added to the reaction mixture, and
the resultant solution was extracted with diisopropyl ether
(20 mL © 3). The organic layer was dried over MgSO4. The
resulting mixture was filtered, and the filtrate was then concen-
trated. Purification of the residue by HPLC afforded the corre-
sponding mono(phenylchalcogeno)alkenes. The product was char-
acterized by comparing its spectral data to those of authentic
samples 6a15 and 6b.16
8.83 (s, 0.35H), 8.43 (s, 0.65H), 7.62-7.19 (m, 10H), 2.46 (s,
0.65 © 3H), 2.36 (s, 0.35 © 3H); 13C NMR (CDCl3, 100 MHz): ¤
198.9, 159.3, 134.1, 133.6, 132.9, 132.1, 131.0, 129.9, 129.6,
129.5, 129.4, 129.4, 128.4, 126.9, 119.9, 22.8; IR (KBr): 687, 745,
1031, 1273, 1403, 1651, 3050 cm¹1; MS m/z 382 (M+ 80Se); Anal.
Calcd for C16H14OSe2: C, 50.54; H, 3.71%. Found: C, 50.67;
1
H, 3.52%. 2e (a mixture of E/Z isomers) H NMR (CDCl3, 400
MHz): ¤ 9.25 (s, 0.75H), 8.88 (s, 0.25H), 3.82 (s, 0.25 © 3H),
3.80 (s, 0.75 © 3H), 3.49-3.27 (m, 8H), 1.84 (t, J = 7.2 Hz,
0.75 © 12H), 1.25 (t, J = 7.2 Hz, 0.25 © 12H); 13C NMR (CDCl3,
100 MHz): ¤ 166.9, 162.6, 161.9, 153.4, 113.2, 52.9, 52.8, 43.2,
42.8, 42.7, 42.5, 42.2, 14.3, 14.2, 14.1, 13.1; IR (KBr): 652, 842,
1071, 1273, 1403, 1667, 1688, 2936, 2975 cm¹1; MS m/z 458.
(M+ 80Se); Anal. Calcd for C14H24N2O4Se2: C, 38.02; H, 5.47; N,
6.33%. Found: C, 38.27; H, 5.74; N, 6.08%.
General Procedure for Cesium Salt-Catalyzed Reaction of
Alkyne with Diphenyl Diselenide in the Presence of Water.
A
DMA (2.5 mL) solution of diphenyl diselenide (314 mg, 1.0
mmol), alkyne (2.0 mmol), H2O (50.0 mmol), and cesium car-
bonate (65 mg, 0.2 mmol) was stirred at 67 °C for 5 h under a
nitrogen atmosphere. After the reaction was complete, aq HCl
(5%) (20 mL) was added to the reaction mixture, and the resultant
solution was extracted with diisopropyl ether (20 mL © 3). The
organic layer was dried over Mg2SO4. The resulting mixture was
filtered, and the filtrate was then concentrated. Purification of the
residue by HPLC afforded the corresponding mono(phenylseleno)-
alkenes. The product was characterized by comparing its spectral
data to those of authentic sample.17
Reaction of Ethyl Propiolate with Cesium Fluoride. A THF
(2.5 mL) solution of ethyl propiolate (0.60 mmol), and cesium
fluoride (90 mg, 0.60 mmol) was stirred at 67 °C for 5 h under a
nitrogen atmosphere. After the reaction was complete, Me3SiCl
(1.5 mmol) was added to the reaction mixture and stirred at 25 °C
for 5 h under a nitrogen atmosphere. H2O (10 mL) was added to the
General Procedure for Cesium Salt-Catalyzed Reaction of
Alkyne with Diphenyl Disulfide. A DMA (2.5 mL) solution of
diphenyl disulfide (218 mg, 1.0 mmol), alkyne (1.0 or 2.0 mmol),
and cesium carbonate (65 mg, 0.2 mmol) was stirred at 67 °C
for 5 h under a nitrogen atmosphere. After the reaction was
complete, aq HCl (5%) (20 mL) was added to the reaction mixture,
and the resultant solution was extracted with diisopropyl ether
(20 mL © 3). The organic layer was dried over MgSO4. The
resulting mixture was filtered, and the filtrate was then concen-
trated. Purification of the residue by HPLC afforded the corre-
sponding vic-bis(phenylthio)alkenes. The product was character-
ized by comparing its spectral data with those of an authentic
sample 3c.1c The structures of the products were assigned by their
1H and 13C NMR, IR, and Mass spectra.
3a (a mixture of E/Z isomers) 1H NMR (CDCl3, 270 MHz):

1174 Bull. Chem. Soc. Jpn. Vol. 82, No. 9 (2009)
Cesium Salt-Catalyzed Addition
reaction mixture, and the resultant solution was extracted with
diisopropyl ether (20 mL © 3). The organic layer was dried over
Mg2SO4. The resulting mixture was filtered, and the filtrate was
then purified by distillation to afford 3-trimethylsilylpropiolate.
The product was characterized by comparing its spectral data with
those of the authentic sample.17
7
Although, Zhangs et al. disclosed that cesium hydroxide
acts as a catalyst for the reaction of diphenyl diselenide with
alkynes, the alkynes were limited to phenyl-substituted alkynes
and acetylene adjacent to alkoxymethyl groups. See: J.-C. Zeng,
R.-L. Lu, X.-H. Xu, J.-K. Fang, B. Zhou, Q.-L. Zhang, Youji.
Huaxue 2004, 24, 1482.
8
On the reaction of ethyl 3-d-propiolate, ethyl 3-(phenyl-
seleno)-2,3-d-acrylate was formed in 6% yield. From this result,
it was suggested that ethyl 3-(phenylseleno)-2,3-d-acrylate was
formed by the deprotonation of terminal alkyne with the vinyl
anion.
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