A simple and stereoselective synthesis of (Z)-1,2-bis-arylselanyl alkenes from alkynes using KF/Al2O3

Article abstract of DOI:10.1016/j.tet.2012.08.055

The title compounds were synthesized by a one-pot reaction of diaryl diselenides with terminal alkynes avoiding the previous preparation of arylselanyl alkynes. The reactions were performed under mild conditions with a range of terminal alkynes using KF/A

Full text of DOI:10.1016/j.tet.2012.08.055

Tetrahedron 68 (2012) 10414e10418
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A simple and stereoselective synthesis of (Z)-1,2-bis-arylselanyl alkenes
from alkynes using KF/Al2O3
*
ꢀ
Renata G. Lara, Paloma C. Rosa, Liane K. Soares, Marcio S. Silva, Raquel G. Jacob, Gelson Perin
LASOL, CCQFA, Universidade Federal de Pelotas, UFPel, P.O. Box 354, 96010-900 Pelotas, RS, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 July 2012
Received in revised form 9 August 2012
Accepted 16 August 2012
Available online 24 August 2012
The title compounds were synthesized by a one-pot reaction of diaryl diselenides with terminal alkynes
avoiding the previous preparation of arylselanyl alkynes. The reactions were performed under mild
conditions with a range of terminal alkynes using KF/Al2O3 and PEG-400 as solvent. The addition of
diaryl diselenides to alkynes occurred stereoselectively to give exclusively (Z)-1,2-bis-arylselanyl alkenes
in good yields. The reaction time was reduced to a few minutes using microwave irradiation and the KF/
Al2O3/PEG-400 system can be reused one time without previous treatment with comparable activity.
Ó 2012 Elsevier Ltd. All rights reserved.
Dedicated to memory of Professor Marcelo
Tiecco
Keywords:
Organoselenium compounds
PEG-400
Vinyl selenides
Microwave irradiation
KF/Al2O3
1. Introduction
selenium species. Recently, the in situ addition of diorganyl dis-
elenides to propargylic alcohols using n-BuLi to afford bis-
In recent years, organoselenium compounds were received
great attention in chemical science because they are attractive as
key intermediate in organic synthesis1,2 and because their in-
teresting fluorescent properties3 and biological activities.4 Beside,
the versatility and applicability of organoselenium compounds in
chemical sciences are well described in a great number of reviews1
and books.2 Between the organoselenium compounds, 1,2-bis-
chalcogenyl alkenes are of special interest, because they can be
used as a versatile precursor to enediynes and other functionalized
olefins.5
1,2-Bis-organylselanyl alkenes have been obtained by the SeeSe
bond addition to alkynes catalyzed by palladium,6 palladium and
microwave irradiation,7 platinum,6c rhodium complex,8 under
photochemical9 or using Ti(i-PrO)4/i-PrMgCl and electrophilic se-
lenium species.10 These protocols afford selectively (Z)-1,2-
bis-organylselanyl alkenes or, in some cases, a mixture of Z and E
isomers and other side products. On the other hand, (E)-1,2-bis-
arylselanyl styrenes were selectively prepared starting from phe-
nylacetylene and diaryl diselenides under solvent-free,11 glycerol12
or in ionic liquid13 using NaBH4 to generate the nucleophilic
phenylselanyl alkenes in good yields and high stereoselectivity
was described.14 The authors observed that the presence of the
acidic hydrogen from hydroxyl group is crucial for the selectivity
control in the addition. However, to our knowledge, reaction under
basic conditions of terminal alkynes with diorganyl diselenide,
avoiding the previous preparation of organylselanyl alkynes to af-
ford (Z)-bis-organylselanyl alkenes remains a challenge in organic
chemistry.15
The development of environmentally benign and clean syn-
thetic protocols using solvents alternative to Volatile Organic
Compounds (VOC’s), such as water, ionic liquids (ILs) and poly-
ethylene glycol (PEG) has increased.16 Despite several advantages,
the use of water is limited due the low solubility of most of organic
substrates, while ILs are expensive and can release hazardous in-
organic residues during recycling. To resolve these inconvenients,
PEG has been proved a promising media for organic synthesis,17
including Heck17a and Mannich17b reactions, cross-coupling,17c,f
N-arylation17g and cycloaddition reactions.17h
On other hand, the use of potassium fluoride supported on
alumina (KF/Al2O3) as a green catalytic system for a number of
transformations has been increased.18 By using KF/Al2O3, the
products can be easily isolated by filtration and the generation of
large amounts of salts at the end of the synthesis, as well as the use
* Corresponding author. E-mail address: gelson_perin@ufpel.edu.br (G. Perin).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.08.055

R.G. Lara et al. / Tetrahedron 68 (2012) 10414e10418
10415
of stoichiometric strong bases, can be avoided. In this sense, KF/
Al2O3 has been employed by our group19 and others20 in various
organic transformations. In this way, as a continuation of our
studies, we report herein the results of the addition of the diorganyl
diselenides to alkynes using KF/Al2O3 for the selective synthesis of
(Z)-1,2-bis-organylselanyl alkenes (Scheme 1).
in Table 2, a range of terminal alkynes worked well and with high
stereoselectivity giving exclusively the (Z)-alkenes. Beside, dif-
ferently to the observed when n-BuLi was employed,14 under our
conditions the presence of a hydroxyl group at the terminal al-
kyne is not essential to the formation exclusively of 1,2-bis-
arylselanyl alkenes, which were obtained even starting from ar-
omatic and aliphatic alkynes. Thus, propargylic alcohol 1b reac-
ted under our conditions with diphenyl diselenide 2a to afford
exclusively (Z)-1,2-bis-(phenylselanyl)prop-2-en-1-ol 3b in 72%
yield (Table 2, entry 3). Similarly, hex-1-yne 1f gave 1,2-
bis(phenylselanyl)hex-1-ene 3h, in 32% yield (Table 2, entry 15).
In general, our results showed that the reactions between diaryl
diselenides and alkynes gave the respective vinyl selenides in
good yields. Thus, diaryl diselenides containing electron-
withdrawing (eCl) or electron-donating groups (eCH3) at the
aromatic ring gave good yields of products 3c,d (Table 2, entries
5e8).
R1Se
R
SeR1
KF/Al2O3 (50%), PEG-400, N2
conventional heating or MW 90 o
(R1Se)2
R
+
C
1a-f
3a-h
2a-c
Scheme 1. General scheme of the reaction.
2. Results and discussion
Initially, we chose phenylacetylene 1a (1.0 mmol) and diphenyl
diselenide 2a (1.0 mmol) as standard starting materials to estab-
lish the best reaction conditions for the synthesis of Z-1,2-bis-
organylselanyl alkenes 3 under N2 atmosphere (Table 1). We ex-
amined the influence of solvent, temperature, amount of KF/Al2O3
(50% m/m), as well as the heating source (oil bath and the use of
focused microwave irradiation). It was found that using 0.04 g of
KF/Al2O3 and PEG-400 (2.0 mL) at room temperature, un-
satisfactory yield of the product 3a was obtained and a great
amount of diphenyl diselenide was recovered (Table 1, entry 1).
When the reaction was performed at 60 ꢀC, a mixture of (Z)- and
(E)-1,2-bis-phenylselanylstyrene 3a and 1-phenylselanyl-2-
phenylethyne 4a was obtained (Table 1, entry 2). Increasing the
temperature to 90 ꢀC, the reaction proceeds smoothly and the
desired product 3a was obtained exclusively in 60% yield (Table 1,
entry 3). To our satisfaction, increasing the amount of KF/Al2O3 to
0.08 g, the desired product 3a was obtained in 83% yield (Table 1,
entry 4).
However, when dimesityl diselenide 2c was used, the desired
1,2-bis-(mesitylselanyl)alkene was obtained in reaction just with
propargylic alcohol 1b, which afforded 3d in 90% yield (Table 2;
entry 7). Surprisingly, phenylacetylene 1a reacted smoothly with 2c
to afford the corresponding 1-mesitylselanyl alkynes 4b in 72%
yield (Scheme 2).
In order to obtain an efficient protocol in terms of energy
efficience, we performed these reactions under focused micro-
wave irradiation (MW) at the same temperature (90 ꢀC). Thus,
the mixture of phenylacetylene 1a (1.0 mmol), diphenyl dis-
elenide 2a (1.0 mmol), KF/Al2O3 (0.08 g) and PEG-400 (2.0 mL)
was irradiated under stirring and fortunately, after 30 min, the
product 3a was selectively obtained in 77% yield (Table 2, entry
2, Method B). To extend the scope of Method B, other terminal
alkynes and diaryl diselenides were irradiated with MW and the
corresponding products 3beh were obtained in comparable
yields after 30 min. As can be seen in Table 2, Method A (con-
ventional heating in an oil bath) is most suitable for phenyl-
acetylene 1a and hex-1-yne 1f. When alkynyl alcohols 1bee
were used, however, Method B (MW heating) provided better
yields.
A reuse study of the KF/Al2O3/PEG-400 system was carried out
for the reaction of 1a with 2a to obtain 3a using MW at 90 ꢀC during
30 min (Method B). After this time, the reaction mixture was di-
luted with hexane/ethyl acetate (90:10). The upper organic phase
was removed and the product was isolated. The remaining KF/
Al2O3/PEG-400 mixture was directly reused for further reactions. It
was observed that a good level of efficiency was maintained in the
second reaction (68% yield of 3a). However, the yield dropped
drastically in the third cycle, with 3a being isolated in only 26%
yield.
Table 1
Investigation of the best conditions to synthesis of 3aa
C6H5
conditions
(C6H5Se)2
C6H5
H
+
C6H5
SeC6H5
+
C6H5Se
SeC6H5
3a
1a
4a
2a
Entry
KF/Al2O3
50% (g)
Solvent
Temperature
(ꢀC)
Yield
of 3a (%)
Ratio
(Z-3a/E-3a)
1
2
3
4
5
6
7
8
0.04
0.04
0.04
0.08
0.08
0.08
0.08
None
PEG-400
PEG-400
PEG-400
PEG-400
Glycerol
None
25
60
90
90
90
25
Reflux
90
Traces
61
60
83
62
80
n.d.
n.d.
d
b
97:3
97:3
15:85
12:88
d
Following, we study the reaction of diphenyl ditelluride 5 with
terminal alkynes under our conditions (Scheme 3). Similarly to the
observed with dimesityl diselenide 2c, the reaction of 5 with
phenylacetylene 1a gave the corresponding 1-phenyltellanyl al-
kyne 6 in good yield (Scheme 3). When alkynyl alcohols were used,
the starting alkynes and ditelluride were recovered.
THF
PEG-400
d
a
Reactions performed using 1a (1 mmol), 2a (1 mmol), and solvent (2.0 mL)
under N2 atmosphere for 6 h.
b
It was observed a mixture of the products 3a/4a in a 57:43 ratio.
A plausible mechanism for the reactions of alkynes with diaryl
diselenides using PEG-400 as solvent for formation of (Z)-1,2-bis-
organylselanyl alkenes is depicted on Scheme 4. Initially, the ex-
perimental evidence supports that occurs the formation of the 1-
organylselanyl-2-organylethyne 4 and selenolate anion.21 In a sec-
ond step, the mechanism is similar to the reaction using ethanol
and the intermediate 7 could be involved in the formation of 3.
When the reaction was performed using internal diphenyl alkyne,
no product was observed, being recovered the starting materials.
Besides, in contrast with our findings, under radical conditions,
the preferential formation of adducts with E-configuration is
observed.9c
In other experiment, we studied the influence of the solvent.
Thus, it was observed that using glycerol instead PEG-400 (Table 1,
entry 5) or under solvent-free conditions (Table 1, entry 6) good
yields of 3a were obtained, but with the preferential formation of
the (E)-isomer. When THF was used as solvent (Table 1, entry 7),
formation of desired product 3a was not detected and the starting
materials were recovered. Similarly, the reaction failed completely
in the absence of KF/Al2O3 (Table 1, entry 8).
Since the best conditions were established, we explored our
method extending the reaction to other terminal alkynes and
diaryl diselenides (Scheme 1, Table 2, Method A). As can be seen

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R.G. Lara et al. / Tetrahedron 68 (2012) 10414e10418
Table 2
Scope of the synthesis of 1,2-bis(arylselanyl)alkenes 3 using KF/Al2O3 and PEG-400a
Entry
Alkyne 1
Diselenide 2
Product 3
Methoda
Yield (%)b
C6H5
Se Se
1
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
83
77
72
70
59
67
90
86
69
77
62
67
81
98
32
22
1a
2a
Se
Se
Se
Se
3a
2
1a
HO
2a
2a
3a
3b
HO
HO
3
1b
3b
4
1b
1b
1b
1b
1b
2a
Cl
Se Se
Cl
5
Cl
Se
Se
Cl
2b
3c
6
2b
3c
OH
7
Se Se
Se
Se
Se
Se
Se
Se
2c
3d
8
2c
2a
2a
2a
2a
2a
2a
2a
2a
3d
3e
3f
HO
HO
HO
9
1c
3e
10
11
12
13
14
15
1c
1d
1e
1f
HO
1d
3f
OH
HO
Se
Se
Se
Se
1e
3g
3g
3h
1f
3h
16
a
Method A: the experiments were performed at 90 ꢀC during 6 h; Method B: the experiments were performed using MW at 90 ꢀC during 30 min.
Yield after purification by column chromatography.
b
H
O PEG
Method A: 72%
)
H
+
Se
Se
C6H5Se SeC6H5
KF/Al2O3
2
Method B: 65%
R
SeC6H5
R
H
2c
1a
4b
R
4
1
C6H5Se
Scheme 2. Synthesis of 1-mesitylselanyl-2-phenylethyne.
δ
O
δ
R
R
H
PEG
Method A: 76%
Te
C6H5Se
SeC6H5
H
+
Te
Te
C6H5Se
SeC6H5
Method B: 51%
3
δ
5
6
7
Scheme 3. Synthesis of 1-phenyltellanyl-2-phenylethyne.
Scheme 4. Mechanism to (Z)-1,2-bis-organylselanyl alkenes 3.
3. Conclusion
stereoselective, avoiding the previous preparation of phenylselanyl
alkynes. The selectivity is extensive to aromatic, aliphatic and
propargyl derivative alkynes. In addition, by this procedure, 1-
mesitylselanyl and 1-phenyltellanyl alkynes were exclusively ob-
tained starting from phenylacetylene. This protocol minimizes the
energy demands and the reaction time could be reduced from
In conclusion, we presented here a new, one-pot methodology
for the preparation of (Z)-1,2-bis(organylselanyl) alkenes starting
from terminal alkynes and diaryl diselenides using KF/Al2O3 and
PEG-400 as solvent. The method is straightforward and highly

R.G. Lara et al. / Tetrahedron 68 (2012) 10414e10418
10417
several hours to few minutes using MW irradiation. The KF/Al2O3/
PEG-400 system was directly re-used one time with a slight de-
clining in yields.
128.5, 127.8, 127.5, 67.5. MS m/z (rel int., %) 370 (Mþ, 17.1), 212 (19.2),
195 (27.2), 157 (43.8), 77 (100.0).
4.3.3. (Z)-2,3-Bis(4-chlorophenylselanyl)prop-2-ene-1-ol
Yield: 0.258 g (59%); yellow oil. 1H NMR (CDCl3, 300 MHz)
¼7.43e7.52 (m, 4H), 7.34 (t, J¼1.2 Hz, 1H), 7.24e7.31 (m, 4H), 4.15
(s, 2H), 1.87 (br s, 1H). 13C NMR (CDCl3, 75 MHz)
(3c).14
4. Experimental section
4.1. General remarks
d
d¼134.5, 134.3,
133.9, 133.6, 133.5, 132.2, 129.6, 129.5, 128.2, 126.7, 67.5.
Hydrogen nuclear magnetic resonance spectra (1H NMR) were
obtained at 200, 300, 400 and 500 MHz on Bruker DPX spectrom-
eters. Spectra were recorded in CDCl3 solutions. Chemical shifts are
reported in parts per million, referenced to tetramethylsilane (TMS)
as the external reference. Data are reported as follows: chemical
4.3.4. (Z)-2,3-Bis(2,4,6-trimethylphenylselanyl)prop-2-ene-1-ol
(3d).24 Yield: 0.409 g (90%); yellow oil. 1H NMR (CDCl3, 500 MHz)
d
¼6.93 (s, 2H), 6.91 (s, 2H), 6.68 (t, J¼1.1 Hz,1H), 3.73 (s, 2H), 2.51 (s,
6H), 2.48 (s, 6H), 2.26 (s, 3H), 2.25 (s, 3H), 1.67 (br s, 1H). 13C NMR
(CDCl3, 125 MHz)
d
¼143.2, 142.6, 138.6, 138.5, 132.5, 128.7, 128.6,
shift (d), multiplicity, coupling constant (J) in hertz and integrated
128.1,126.7,125.4, 66.5, 24.4, 24.2, 20.9. MS m/z (rel int., %) 452 (Mþ,
intensity. Carbon-13 nuclear magnetic resonance spectra (13C NMR)
were obtained at 75 and 125 MHz on Bruker DPX spectrometers.
Spectra were recorded in CDCl3 solutions. Chemical shifts are re-
ported in ppm, referenced to the solvent peak of CDCl3. Mass
spectra (MS) were measured on a Shimadzu GCeMS-QP2010 mass
spectrometer. Column chromatography was performed using
Merck Silica Gel (230e400 mesh). Thin layer chromatography (TLC)
was performed using Merck Silica Gel GF254, 0.25 mm thickness.
For visualization, TLC plates were either placed under ultraviolet
light, or stained with iodine vapor, or acidic vanillin. All solvents
were used as purchased unless otherwise noted. Terminal alkynes
and PEG-400 were obtained from Aldrich and used without further
purification. Microwave reactions were conducted using a CEM
Discover, mode operating systems working at 2.45 GHz, with
a power programmable from 1 to 300 W.
9.3), 223 (12.6), 198 (20.4), 119 (100.0).
4.3.5. (Z)-2-Methyl-3,4-bis(phenylselanyl)but-3-ene-2-ol
(3e).14
¼7.62
Yield: 0.275 g (69%); yellow oil. 1H NMR (CDCl3, 300 MHz)
d
(s, 1H), 7.48e7.57 (m, 4H), 7.21e7.32 (m, 6H), 2.18 (br s, 1H), 1.45 (s,
6H). 13C NMR (CDCl3, 75 MHz)
d
¼139.0, 136.8, 133.2, 130.7, 130.3,
129.9, 129.3, 129.3, 127.7, 126.5, 75.8, 29.4. MS m/z (rel int., %) 398
(Mþ, 13.0), 380 (10.3), 157 (50.0), 77 (100.0).
4.3.6. (Z)-3-Methyl-1,2-bis(phenylselanyl)pent-1-ene-3-ol
(3f). Yield: 0.255 g (62%); yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.57 (s, 1H), 7.49e7.58 (m, 4H), 7.18e7.32 (m, 6H), 2.08 (br s, 1H),
1.60e1.83 (m, 2H), 1.39 (s, 3H), 0.85 (t, J¼7.5 Hz, 3H). 13C NMR
(CDCl3, 125 MHz)
d¼138.1, 137.2, 133.1, 130.8, 130.3, 130.2, 129.3,
129.2, 127.7, 126.6, 78.4, 34.2, 26.4, 8.4. MS m/z (rel int., %) 412 (Mþ,
7.7), 182 (10.7), 157 (42.4), 77 (74.4), 43 (100.0). HRMS (ESI): m/z
calcd for C18H20OSe2 [MþNa]þ: 434.9742; found: 434.9739.
4.2. General procedure for the preparation of alumina-sup-
ported potassium fluoride22
4.3.7. (Z)-1-[1,2-Bis(phenylselanyl)vinyl]cyclohexanol (3g).6c Yield:
0.355 g (81%); yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.63 (s, 1H),
7.53e7.56 (m, 2H); 7.47e7.51 (m, 2H), 7.17e7.32 (m, 6H), 1.86 (br s,
1H), 1.51e1.76 (m, 10H). 13C NMR (CDCl3, 75 MHz)
To a 50 mL beaker was added alumina (3.0 g of Al2O3 90,
0.063e0.200 mm, Merck), KF$2H2O (3.0 g) and water (5 mL). The
suspension was stirred for 1 h at 65 ꢀC, dried at 80 ꢀC for 1 h and for
an additional 4 h at 300 ꢀC in an oven and then cooled in a desic-
cator. The content of KF is about 50% (m/m).
d¼140.0, 137.2,
133.2, 130.9, 130.5, 129.8, 129.3, 129.2, 127.7, 126.4, 76.3, 36.7, 25.4,
22.0. MS m/z (rel int., %) 438 (Mþ, 5.4), 263 (13.5), 182 (49.4), 157
(34.7), 77 (100.0).
4.3. General procedure for the preparation of compounds
3aeh through Method A
4.3.8. (Z)-1,2-Bis(phenylselanyl)hex-1-ene (3h).24 Yield: 0.127 g
(32%); yellow oil. 1H NMR (CDCl3, 400 MHz)
d¼7.51e7.57 (m, 4H),
To a mixture of terminal alkyne1 (1 mmol)anddiaryl diselenide 2
(1 mmol) in PEG-400 (2.0 mL) under N2 atmosphere, KF/Al2O3 50%
(0.08 g) was added at room temperature under stirring. Then, the
mixture was heated slowly to 90 ꢀC and the reaction progress was
followed by TLC. After 6 h water (3 mL) was added and the mixture
was extracted with ethyl acetate (3ꢁ5 mL). The organic layers were
combined, washed with brine solution (3 mL) and dried with MgSO4.
The solvent was removed under vacuum and the product was iso-
lated by column chromatography using hexane/ethyl acetate as el-
uent. Spectral data of the products prepared are listed below.
7.25e7.32 (m, 6H), 6.93 (s, 1H), 2.28 (t, J¼7.2 Hz, 2H), 1.47 (qui,
J¼7.2 Hz, 2H), 1.23 (sex, J¼7.2 Hz, 2H), 0.82 (t, J¼7.2 Hz, 3H). MS m/z
(rel int., %) 396 (Mþ, 17.0), 239 (14.0), 183 (48.4), 157 (41.8), 81
(100.0).
4.4. General procedure for the preparation of compounds
3aeh through Method B
In a 10 mL glass vial equipped with a small magnetic stirring bar,
containing a solution of terminal alkyne 1 (1 mmol) and diaryl
diselenide 2 (1 mmol) in PEG-400 (2.0 mL) under N2 atmosphere,
KF/Al2O3 50% (0.08 g) was added at room temperature. The mixture
was then irradiated in a focused microwaves reactor (CEM) at 90 ꢀC,
using an irradiation power of 50 W and pressure of 50 psi. After
stirring for 30 min (Table 2), the products were isolated as de-
scribed above on Method A.
Reuse: After stirring for 30 min under MW as described above,
the reaction mixture was washed with a mixture of hexane/ethyl
acetate (90:10; 5ꢁ1 mL) and the upper organic phase was sepa-
rated from KF/Al2O3/PEG-400. The product was isolated according
procedure above. The mixture KF/Al2O3/PEG-400 was dried under
vacuum and reused for further reactions.
4.3.1. (Z)-1,2-Bis-phenylselanyl styrene (3a).23 Yield: 0.345 g (83%);
yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.59e7.65 (m, 2H); 7.60 (s,
1H); 7.48e7.52 (m, 2H); 7.36e7.40 (m, 2H); 7.30e7.34 (m, 3H);
7.12e7.24 (m, 6H). 13C NMR (CDCl3, 75 MHz)
d
¼140.5, 136.1, 133.2,
131.4,131.0,130.8,130.3,129.4,129.1,128.3, 127.8,127.5,127.3,126.6.
MS m/z (rel int., %) Z isomer: 416 (Mþ, 14.1), 259 (43.1), 179 (100.0),
77 (72.6); E isomer: 416 (Mþ, 17.1), 259 (45.1), 178 (100.0), 77 (64.1).
4.3.2. (Z)-2,3-Bis(phenylselanyl)prop-2-en-1-ol (3b).6c Yield: 0.266 g
(72%); yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.44e7.52 (m, 4H);
7.31 (s, 1H); 7.17e7.24 (m, 6H); 4.06 (s, 2H); 1.91 (br s, 1H). 13C NMR
(CDCl3, 75 MHz)
¼133.5, 133.1, 132.3, 132.0, 130.2, 129.4, 129.3,
d

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P.; Beletskaya, I. P.; Aleksandrov, G. G.; Eremenko, I. L. Organometallics 2003, 22,
1414; (d) Cai, M.; Wang, Y.; Hao, W. Green Chem. 2007, 9, 1180; (e) Ananikov, V.
P.; Beletskaya, I. P. Russ. Chem. Bull. Int. Ed. 2004, 53, 561; (f) Ananikov, V. P.;
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Phosphorus, Sulfur Silicon Relat. Elem. 1998, 136e138, 591.
4.5. General procedure for the preparation of chalcogeno al-
kynes 4b and 6
Method A: To a mixture of phenylacetylene 1a (1 mmol) and
diaryl dichalcogenide (1 mmol) in PEG-400 (2.0 mL) under N2 at-
mosphere, KF/Al2O3 50% (0.08 g) was added at room temperature.
Then, the mixture was heated slowly to 90 ꢀC and the reaction
progress was followed by TLC. After stirring for 6 h the products
were isolated as described above, for 3. Method B: The mixture was
irradiated in a focused microwaves reactor (CEM) at 90 ꢀC, using an
irradiation power of 50 W and pressure of 50 psi. After stirring for
30 min, the products were isolated as described above. Spectral
data of the products prepared are listed below.
7. Ananikov, V. P.; Orlov, N. V.; Beletskaya, I. P. Russ. Chem. Bull., Int. Ed. 2005,
54, 576.
8. Arisawa, M.; Kozuki, Y.; Yamaguchi, M. J. Org. Chem. 2003, 68, 8964.
9. (a) Ogawa, A.; Yokoyama, H.; Yokoyama, K.; Masawaki, T.; Kambe, N.; Sonoda,
N. J. Org. Chem. 1991, 56, 5721; (b) Ogawa, A.; Ogawa, I.; Sonoda, N. J. Org. Chem.
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10. Silveira, C. C.; Cella, R.; Vieira, A. S. J. Organomet. Chem. 2006, 691, 5861.
4.5.1. 1-Mesitylselanyl-2-phenylethyne (4b).25 Yield: 0.216 g (72%);
yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.35e7.37 (m, 2H),
7.24e7.26 (m, 3H), 6.95 (s, 2H), 2.62 (s, 6H), 2.27 (s, 3H). 13C NMR
(125 MHz)
d
¼142.2, 139.1, 131.5, 129.0, 128.1, 128.0, 125.6, 123.6,
97.3, 71.3, 24.1, 20.9. MS m/z (rel int., %) 300 (Mþ, 3.4), 219 (100.0),
~
11. Perin, G.; Jacob, R. G.; Dutra, L. G.; Azambuja, F.; Santos, G. F. F.; Lenardao, E. J.
Tetrahedron Lett. 2006, 47, 935.
12. Lenardao, E. J.; Silva, M. S.; Sachini, M.; Lara, R. G.; Jacob, R. G.; Perin, G. Arkivoc
77 (8.4).
~
2009, xi, 221.
4.5.2. 1-Phenyltellanyl-2-phenylethyne (6).26 Yield: 0.234 g (76%);
~
13. (a) Lenardao, E. J.; Dutra, L. G.; Saraiva, M. T.; Jacob, R. G.; Perin, G. Tetrahedron
dark yellow oil. 1H NMR (CDCl3, 300 MHz)
d
¼7.67e7.75 (m, 2H),
Lett. 2007, 48, 8011; (b) Lenardao, E. J.; Gonc¸ alves, L. C. C.; Mendes, S. R.; Saraiva,
~
7.43e7.48 (m, 2H), 7.24e7.35 (m, 6H). 13C NMR (CDCl3, 75 MHz)
M. T.; Alves, D.; Jacob, R. G.; Perin, G. J. Braz. Chem. Soc. 2010, 21, 2093.
14. Moro, A. V.; Nogueira, C. W.; Barbosa, N. B. V.; Menezes, P. H.; Rocha, J. B. T.;
Zeni, G. J. Org. Chem. 2005, 70, 5257.
15. (a) Potapov, V. A.; Amosova, S. V.; Shestakova, V. Y.; Starkova, A. A.; Zhnikin, A.
R. Sulfur Lett. 1997, 21, 103; (b) Potapov, V. A.; Amosova, S. V.; Shestakova, V. Y.
Phosphorus, Sulfur Silicon Relat. Elem. 1998, 136e138, 205.
16. (a) Wasserscheid, P.; Welton, T. Ionic Liquids in Synthesis; Wiley-VCH: New York,
NY, 2002; (b) Jain, N.; Kumar, A.; Chauhan, S.; Chauhan, S. M. S. Tetrahedron
2005, 61, 1015; (c) Dupont, J.; Souza, R. F.; Suarez, P. A. Z. Chem. Rev. 2002, 102,
3667; (d) Welton, T. Chem. Rev. 1999, 99, 2071; (e) Davis, J. H., Jr.; Fox, P. A. Chem.
Commun. 2003, 1209; (f) Wassercheid, P.; Keim, W. Angew. Chem., Int. Ed. 2000,
39, 3772.
d
¼137.9, 135.1, 131.9, 129.7, 128.6, 128.2, 127.9, 123.3, 113.1, 47.4. MS
m/z (rel int., %) 308 (Mþ, 4.7), 207 (12.4), 178 (100.0), 77 (23.8).
Acknowledgements
The authors are grateful to FAPERGS and CNPq (PRONEX 10/
0005-1, PRONEM 11/2026-4 and PqG 11/0719-3), CAPES and FINEP
for the financial support.
17. (a) Chandrasekhar, S.; Narsihmulu, C.; Sultana, S. S.; Reddy, N. R. Org. Lett. 2002,
4, 4399; (b) Kidwai, M.; Bhatnagar, D.; Mishra, N. K.; Bansal, V. Catal. Commun.
2008, 9, 2547; (c) Reddy, G. C.; Balasubramanyam, P.; Salvanna, N.; Das, B. Eur. J.
Org. Chem. 2012, 471; (d) Zhang, Q.; Chen, J.-X.; Gao, W.-X.; Ding, J.-C.; Wu, H.-Y.
Appl. Organomet. Chem. 2010, 24, 809; (e) Cho, C. S.; Tran, N. T. Catal. Commun.
2009, 11, 191; (f) She, J.; Jiang, Z.; Wang, Y. Tetrahedron Lett. 2009, 50, 593; (g)
Colacino, E.; Villebrun, L.; Martinez, J.; Lamaty, F. Tetrahedron 2010, 66, 3730; (h)
Kouznetsov, V. V.; Arenas, D. R. M. Tetrahedron Lett. 2009, 50, 1546; (i) Perin, G.;
Borges, E. L.; Alves, D. Tetrahedron Lett. 2012, 53, 2066.
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