Glycerol/CuI/Zn as a recyclable catalytic system for synthesis of vinyl sulfides and tellurides

Article abstract of DOI:10.1016/j.tetlet.2013.04.119

A convenient approach to the Cu-catalyzed coupling of diphenyl disulfide and diphenyl ditelluride with vinyl bromides using a recyclable catalytic system and glycerol as a green solvent is described. This protocol was efficiently used in the preparation of vinyl sulfides and vinyl tellurides with a variety of substituents in good yields and stereoselectively. The solvent/catalyst system was directly reused for four cycles without loss of activity.

Full text of DOI:10.1016/j.tetlet.2013.04.119

Tetrahedron Letters 54 (2013) 3475–3480
Contents lists available at SciVerse ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Glycerol/CuI/Zn as a recyclable catalytic system for synthesis of vinyl sulfides
and tellurides
Lóren C. C. Gonçalves, David B. Lima, Pedro M. Y. Borba, Gelson Perin, Diego Alves, Raquel G. Jacob,
⇑
Eder J. Lenardão
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:
A convenient approach to the Cu-catalyzed coupling of diphenyl disulfide and diphenyl ditelluride with
vinyl bromides using a recyclable catalytic system and glycerol as a green solvent is described. This pro-
tocol was efficiently used in the preparation of vinyl sulfides and vinyl tellurides with a variety of sub-
stituents in good yields and stereoselectively. The solvent/catalyst system was directly reused for four
cycles without loss of activity.
Received 12 March 2013
Revised 24 April 2013
Accepted 26 April 2013
Available online 3 May 2013
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Glycerol
Vinyl sulfides
Vinyl tellurides
Cross-coupling
Organochalcogen compounds have become intensively studied
due to their biological and pharmacological activities,1 use as effi-
cient polydentate ligands for designing metal complexes,2 crystal-
line metal chalcogenide clusters,3 and versatile building blocks for
organic synthesis.4 Among the organochalcogenium species, vinyl
chalcogenides are useful synthons in organic reactions, particularly
in the synthesis of carbonyl compounds and for stereospecific syn-
thesis of substituted alkenes.5 In this context, vinyl sulfides and vi-
nyl tellurides constitute very useful intermediates, because they
combine the reactivity of both the organochalcogen group and
the carbon–carbon double bond.6,7
raised a growing interest in the search for green solvents from
renewable resources.9 The peculiar physical and chemical proper-
ties of glycerol, such as high boiling point, polarity, low toxicity,
biodegradability, no flammability, and ready availability from
renewable feedstock, turn it a strong candidate to a safe, renewable
solvent.10 The use of glycerol as a solvent in organic synthesis has
grown considerably in recent years and several successful exam-
ples have been described by us11 and others.12 These include Pd-
catalyzed Heck and Suzuki cross-couplings, base- and acid-pro-
moted condensations, oxidation, catalytic hydrogenation, and
asymmetrical reduction.11,12
Among various methods to synthesize selectively vinyl sulfides
and tellurides is the hydrochalcogenation of alkynes using thiols or
the respective chalcogenolate anion generated in situ.6,7 Although
an atom-economic procedure, the hydrochalcogenation is suitable
for a restricted number of terminal and activated alkynes. Alterna-
tively, vinyl chalcogenides can be obtained by cross-coupling of
diaryl dichalcogenides with vinyl halides, however, this reaction
generally requires the use of expensive noble metals and high tem-
Recently, we have described a successful synthesis of vinyl
selenides by the Cu-catalyzed cross-coupling of diaryl diselenides
and vinyl bromides using CuI/Zn/glycerol as catalytic system
(Scheme 1).13 In view of our interest in the development of new
and cleaner methods for the preparation of organochalcogenium
compounds, we present here our results on the conversion of
(E)- and (Z)-vinyl bromides to the respective (E)- and (Z)-vinyl sul-
fides and vinyl tellurides using the catalytic system CuI/Zn/glycerol
(Scheme 1).14
For the reaction of diaryl diselenides with vinyl bromides using
glycerol as solvent it was found that the best conditions for the
coupling reaction consist of stirring a mixture of diaryl diselenide
(0.3 mmol) and bromostyrene (0.6 mmol) in the presence of CuI
(5 mol %), Zn dust (0.6 mmol) as additive, glycerol as solvent
(1.5 mL) at 110 °C (oil bath), and under N2 atmosphere.13 Aiming
to extend this efficient protocol to other chalcogenium species,
we tested the cross-coupling reaction using (E)-b-bromostyrene
1a and diphenyl disulfide 2a as starting materials. After stirring
perature, restricting its application.8 A wide range of metal cata-
8c
lysts including palladium,
lanthanum,8f and copper-based8g,h
have been exploited for these cross-coupling reactions. However,
the use of copper catalysts remains quite rare despite the clear
advantage in cost-effectiveness.
On the other hand, in view of the widespread use of solvents in
nearly all of the chemical and pharmaceutical industries, it has
⇑
Corresponding author. Tel./fax: +55 5332757533.
E-mail address: lenardao@ufpel.edu.br (E.J. Lenardão).
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.04.119

3476
L. C. C. Gonçalves et al. / Tetrahedron Letters 54 (2013) 3475–3480
Br
YAr
ArYYAr
R
R
CuI (5%), Zn
glycerol
or
or
110 oC, N2
Y = S, Te
ArYYAr
R
R
Br
YAr
Y = Se, ref. 13; Y = S and Te, this work
Scheme 1. General scheme of the reaction.
for 4 h at 110 °C, (E)-b-(phenylthio)styrene 3a was obtained in 75%
yield, a result not so good compared with the selenium analogous,
which provided (E)-b-(phenylseleno)styrene in 95% yield. Thus,
trying to improve the yield of 3a, we screened several conditions
for this cross-coupling reaction, varying the reaction time, catalyst
loading, temperature, use of additive, and inert atmosphere (Table
1). No substantial increase in yield was observed in all the tested
variations, even using a larger amount of catalyst or a longer reac-
tion time (Table 1, entries 4 and 5).
Remarkably, the formation of 3a was not observed in the ab-
sence of CuI and when zinc was omitted from the reaction mixture,
the yield was only 42% (Table 1, entries 8 and 9). We also observed
that temperature and N2 atmosphere are crucial to ensure a good
yield of 3a (Table 1, entries 7 and 10). In addition, when the reac-
tions were performed using other copper species with or without
zinc dust, poor yields of desired product 3a were obtained (Table
1, entries 12–14).
This protocol was then extended to the cross-coupling of diaryl
disulfide 2a–d with various readily accessible (E)- and (Z)-b-
bromostyrenes 1a–g to expand the scope of the reaction (Table 2,
entries 1–10). As can be seen in Table 2, a range of b-bromosty-
renes were successfully used, affording the respective vinyl sul-
fides in good yields and with high stereoselectivity. Thus, (E)-4-
methoxy-b-bromostyrene 1b reacted under our conditions with di-
phenyl disulfide 2a to afford exclusively (E)-4-methoxy-b-(phenyl-
thio)styrene 3b in 85% yield after 2 h (Table 2, entry 2). It was
verified that the reaction works well in high level of stereoselectiv-
ity also with (Z)-b-bromostyrene 1f which gave (Z)-b-(phenyl-
thio)styrene 3f in 70% yield after 6 h (Table 2, entry 6). Besides,
diaryl disulfides containing electron-withdrawing or electron-
donating groups at the aromatic ring also gave good yields of prod-
ucts 3h–j (Table 2, entries 8–10).
In recent years, vinyl tellurides have a peculiar reactivity face to
diversity of metals and are valuable synthons for the selective
preparation of substituted alkenes in total organic synthesis.15 In
this sense, the development of selective and general methods to
prepare vinyl tellurides with total control on the stereochemistry
of the double bond is a critical challenge to synthetic organic
chemists. Thus, according to our studies, the CuI/Zn/glycerol sys-
tem was efficiently used for the CATe bond formation via cross-
coupling reaction of diaryl ditellurides 2e–f with b-bromostyrenes
(Table 2, entries 11–18). Similar to the reaction observed with di-
phenyl disulfide 2a, styryl bromides with both, electron-donating
and electron-withdrawing groups at the aromatic ring, such as
methoxyl, methyl, and chloro, afforded the corresponding vinyl tel-
lurides in good yields and selectively (Table 2, entries 12–15).
When (Z)-b-bromostyrenes were used, a high degree of retention
on the configuration of the double bond was observed (Table 2, en-
tries 16 and 17). It was also verified that bis(4-methoxyphenyl)
ditelluride 2f easily coupled with (E)-b-bromostyrene 1a, affording
after 24 h exclusively (E)-b-(4-methoxyphenyltelluro)styrene 3r in
75% yield (Table 2, entry 18).
Additionally, a reuse study of the CuI/Zn/glycerol system was
carried out for the reaction of 1a with 2a to obtain 3a. After stirring
at 110 °C during 4 h, the reaction mixture was diluted and ex-
tracted with a mixture of hexane/ethyl acetate 95/5 (3 Â 3.0 mL).
Table 1
Optimization of the synthesis of (E)-b-(phenylthio)styrene 3aa
Br
S
S
glycerol
conditions
+
S
1a
3a
2a
Entry
CuI (mol %)
Zinc (mmol)
Temp (°C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
1
3
5
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
—
0.6
0.3
0.6
0.6
—
110
110
110
110
110
110
60
110
110
110
110
110
110
110
24
24
4
23
25
75
77
70
73
56
NR
42
52
54
25
15
6
5
24
24
24
24
24
24
24
24
24
24
24
10
20
5
—
5
9
10b
11
12
13
14
5
5
5c
5d
5d
a
b
c
Reactions performed using (E)-b-bromostyrene 1a (0.6 mmol), diphenyl disulfide 2a (0.3 mmol), and glycerol (1.5 mL) under N2 atmosphere.
The reaction was performed in an open atmosphere.
CuCl2 was used as a catalyst.
d
Copper powder was used as a catalyst.

L. C. C. Gonçalves et al. / Tetrahedron Letters 54 (2013) 3475–3480
3477
Table 2
Scope of the synthesis of vinyl sulfides 3a–j and vinyl tellurides 3k–ra
Y
Br
R'
CuI (5%), Zn, glycerol
110 oC, N2
R
Y
R'
R
+
Y
R'
3a-r
1a-g
2a f
-
Entry
1
Vinyl bromide 1 (ratio E:Z)
Dichalcogenide 2
Product 3
Time (h)
4
Yieldb (%)
75
Ratioc (E:Z)
Br
S
S
S
97:3
100:0
94:6
3a
1a (93:7)
2a
Br
S
S
S
2
3
4
2
3
3
85
78
70
CH3O
3b
CH3O
1b (99:1)
2a
Br
S
S
S
CH3
CH3
3c
1c (99:1)
2a
Br
S
S
S
99:1
Cl
Cl
3d
1d (99:1)
2a
OCH3
Br
S
S
S
5
6
4
6
74
70
94:6
OCH3
1e (99:1)
2a
3e
S
S
S
Br
0:100
1f (1:99)
3f
OCH3
2a
OCH3
S
S
7
6
60
13:87
Br
S
2a
1g (36:64)
3g
Br
S
S
S
CH3O
OCH3
8
24
8
62
75
60
85
100:0
100:0
85:15
100:0
S
3h
2b
OCH3
CH3
Cl
1a (93:7)
Br
S
CH3
Cl
S
9
CH3
3i
1a (93:7)
2c
Br
S
S
10
11
24
20
Cl
S
3j
2d
1a (93:7)
Br
Te
Te
Te
Te
Te
3k
1a (93:7)
2e
Te
Br
12
13
4
4
89
65
99:1
97:3
Te
CH3O
CH3
3l
Te
CH3O
1b (99:1)
2e
Br
Te
3m
CH3
1c (99:1)
2e
(continued on next page)

3478
L. C. C. Gonçalves et al. / Tetrahedron Letters 54 (2013) 3475–3480
Table 2 (continued)
Entry
Vinyl bromide 1 (ratio E:Z)
Br
Dichalcogenide 2
Product 3
Time (h)
3
Yieldb (%)
72
Ratioc (E:Z)
Te
Te
Te
14
98:2
Te
Cl
3n
Cl
1d (99:1)
2e
OCH3
Br
Te
15
16
24
24
75
60
96:4
Te
OCH3
1e (99:1)
2e
3o
Te
Te
Br
Br
Te
Te
0:100
1f (1:99)
2e
3p
OCH3
OCH3
Te
17
18
24
24
67
75
24:76
100:0
2e
Te
1g (36:64)
3q
Br
Te
CH3O
Te
Te
OCH3
3r
2f
OCH3
1a (93:7)
a
b
c
Reactions performed in the presence of vinyl bromide 1a–g (0.6 mmol), diaryl dichalcogenide 2a–f (0.3 mmol), Zn dust (0.6 mmol), and 5 mol % of CuI in glycerol (1.5 mL).
Yields are given for isolated products.
Determined by GC/MS and by 1H NMR of crude reaction products.
Table 3
Reuse of catalytic system CuI/Zn/glycerol
CuI (5%), Zn
glycerol
S
Br
S
+
S
110 °C, N2
1a
3a
2a
Cycle
Time
Yield of 3aa (%)
1
2
3
4
5
6
4
4
4
4
4
75
73
72
70
64
56
24
a
Yields are given for isolated products.
The upper organic phase was removed, the solvent evaporated and
the product 3a was isolated. The remaining inferior phase contain-
ing a mixture of CuI/Zn/glycerol was dried under vacuum and di-
rectly reused for further reactions, simply by adding more
reagents 1a and 2a. (E)-b-(Phenylthio)styrene 3a was obtained in
75%, 73%, 72%, and 70% yields after successive cycles showing a
good level of efficiency. After four runs, the efficiency of catalytic
system was reduced and the yields decreased in the fifth and sixth
cycles (Table 3).16
We believe that a plausible mechanism of this reaction could in-
volve the initial reduction of Cu(I) to Cu(0) by metal zinc; follow-
ing, which Cu(0) undergoes an oxidative addition with diaryl
dichalcogenide (ArYYAr) to form an intermediate, (ArY)2Cu(II)
(Scheme 2). After reduction by Zn, this intermediate leads to ArY-
Cu(I), which reacts with b-bromostyrene to give the respective b-
(arylchalcogeno)styrene via a ‘transitory’ Cu(III) intermediate.
The Zn(YAr)2 formed after the reduction of Cu(YAr)2 by Zn reacts
with CuI to give more ArYCu(I), with both ArY moieties of ArYYAr
being used in the overall reaction. A similar mechanism is believed
to be involved in the Cu(0) nanoparticle-catalyzed cross couplings
of vinyl bromides with diphenyl diselenide.8d
YAr
1/2 Zn
or
1/2 ZnX2
X = Br, I
YAr
CuX
vinyl
ArY Cu
Cu(0)
Br
ArYYAr
vinyl Br
ArY Cu YAr
ArYCu(I)
CuX
1/2 Zn
1/2 Zn(YAr)2
Scheme 2. Probable mechanism.

L. C. C. Gonçalves et al. / Tetrahedron Letters 54 (2013) 3475–3480
3479
12. (a) Johnson, D. T.; Taconi, K. A. Environ. Prog. 2007, 26, 338; (b) Bakhrou, N.;
Lamaty, F.; Martinez, J.; Colacino, E. Tetrahedron Lett. 2010, 51, 3935; (c) Li, M.;
Chen, C.; He, F.; Gu, Y. Adv. Synth. Catal. 2010, 352, 519; (d) Francos, J.;
Cadierno, V. Green Chem. 2010, 12, 1552.
13. Gonçalves, L. C.; Fiss, G. F.; Perin, G.; Alves, D.; Jacob, R. G.; Lenardão, E. J.
Tetrahedron Lett. 2010, 51, 6772.
In conclusion, we have developed a mild and efficient method
for the stereoselective synthesis of vinyl sulfides and vinyl tellu-
rides in very good yields using a catalytic, recyclable, and eco-
friendly system. The notable advantages offered by this method in-
clude stereoselectivity for Z- and E-styryl bromides, general appli-
cability to a wide variety of substrates, and easy recovering and
reusing of the catalytic system. These remarkable characteristics
made this new protocol economically and eco-friendly attractive,
inexpensive, and offering the possibility of performing the reaction
in the absence of toxic organic solvents and heavy metals.
14. General procedure for the cross-coupling reaction: The mixture of CuI
(0.03 mmol, 5 mol %) and Zn dust (0.6 mmol) in glycerol (1.5 mL) was stirred
under nitrogen atmosphere for 30 min at 110 °C. After that, the reaction vessel
was cooled to room temperature and diaryl dichalcogenide 2 (0.3 mmol) and
vinyl bromide 1 (0.6 mmol) were added. The reaction mixture was stirred at
110 °C and the reaction progress was followed by TLC. After the time indicated
in Table 2, the solution was cooled to room temperature, diluted with ethyl
acetate (20 mL), and washed with sat. NH4Cl (3 Â 20 mL). The organic layer
was separated, dried over MgSO4 and concentrated under vacuum. The crude
product was purified by flash chromatography on silica gel using ethyl acetate/
hexanes as eluent. Spectral data of the products prepared are listed below.
(E)-(styryl)(phenyl)sulfide (3a).8g Yield: 0.095 g (75%). 1H NMR (CDCl3,
200 MHz) d = 7.39 (d, J = 7.6 Hz, 2H), 7.34–7.18 (m, 8H), 6.88 (d, J = 15.2 Hz,
1H), 6.69 (d, J = 15.2 Hz, 1H). 13C NMR (CDCl3, 100 MHz) d = 135.1, 132.5, 131.7,
129.7, 129.3, 129.1, 128.6, 127.6, 127.5, 127.3, 126.9, 126.0, 123.3, 119.3. MS
m/z (rel int.,%) 212 (100), 211 (48), 178 (40), 121 (38), 91 (19), 77 (31). (E)-(4-
methoxystyryl)(phenyl)sulfide (3b).8c Yield: 0.123 g (85%). 1H NMR (CDCl3,
400 MHz) d = 7.43–7.37 (m, 2H), 7.33–7.13 (m, 5H), 6.87–6.78 (m, 2H), 6.69 (d,
J = 15.4 Hz, 1H), 6.62 (d, J = 15.4 Hz, 1H), 3.73 (s, 3H). 13C NMR (CDCl3,
100 MHz) d = 164.9, 159.3, 135.9, 132.7, 129.2, 129.0, 127.3, 126.5, 120.0,
114.1, 55.3. MS m/z (rel int.,%) 242 (70), 211 (26), 207 (36), 197 (35), 91 (31), 77
(100). (E)-(4-methylstyryl)(phenyl)sulfide (3c).8g Yield: 0.105 g (78%). 1H NMR
(CDCl3, 300 MHz) d = 7.64–7.60 (m, 2H), 7.45–7.02 (m, 8H), 6.73 (d, J = 15.4 Hz,
1H), 6.64 (d, J = 15.4 Hz, 1H), 2.24 (s, 3H). 13C NMR (CDCl3, 75 MHz) d = 21.2,
121.8, 125.9, 126.7, 129.0, 129.4, 129.5, 132.4, 133.7, 135.6, 137.5. MS m/z (rel
int.,%) 226 (61), 211 (40), 207 (24), 121 (31), 115 (62), 77 (68), 40 (100). (E)-(4-
chlorostyryl)(phenyl)sulfide (3d).8e Yield: 0.103 g (70%). 1H NMR (CDCl3,
200 MHz) d = 6.51 (d, J = 15.6 Hz, 1H); 6.86 (d, J = 15.6 Hz, 1H); 7.23–7.43 (m,
9H). 13C NMR (CDCl3, 50 MHz) d = 124.6, 127.3, 127.2, 128.8, 129.2, 129.7,
130.2, 133.1, 134.7, 135.0. MS m/z (rel int.,%) 246 (18), 245 (6), 242 (100), 227
(20), 211 (36), 197 (51), 165 (43), 77 (32). (E)-(2-methoxystyryl)(phenyl)sulfide
(3e).17 Yield: 0.107 g (74%). 1H NMR (CDCl3, 300 MHz) d = 7.56–7.49 (m, 3H);
7.41–7.36 (m, 6H); 6.82 (d, J = 15.5 Hz, 1H); 6.69 (d, J = 15.5 Hz, 1H); 3.78 (s,
3H). 13C NMR (CDCl3, 50 MHz) d = 138.3, 138.9, 135.9, 135.5, 133.6, 133.1,
132.8, 132.5, 129.8, 129.4, 127.7, 124.1, 55.3. MS m/z (rel int.,%) 242 (16), 210
(100), 195 (19), 120 (22), 109 (12), 77 (21). (Z)-(styryl)(phenyl)sulfide (3f).8c
Yield: 0.089 g (70%). 1H NMR (CDCl3, 300 MHz) d = 7.58–7.46 (m, 2H); 7.44–
7.24 (m, 8H); 6.63 (d, J = 10.4 Hz, 1H); 6.53 (d, J = 10.4 Hz, 1H). 13C NMR (CDCl3,
75 MHz) d = 136.5, 135.2, 125.9, 132.9, 131.7, 130.0, 129.8, 129.1, 128.6, 127.6,
123.3. MS m/z (rel int.,%) 212 (100), 211 (51), 179 (30), 121 (46), 91 (25), 77
(44). (Z)-(2-methoxystyryl)(phenyl)sulfide (3g).18 Yield: 0.087 g (60%). 1H NMR
(CDCl3, 300 MHz) d = 7.66–7.54 (m, 3H); 7.49–7.28 (m, 6H); 6.77 (d, J = 10.3 Hz,
1H); 6.52 (d, J = 10.3 Hz, 1H); 3.82 (s, 3H). 13C NMR (CDCl3, 100 MHz) d = 136.4,
130.4, 129.7, 129.0, 128.7, 128.2, 126.8, 125.9, 125.6, 122.6, 120.4, 117. 9, 55.4.
MS m/z (rel int.,%) 242 (100), 241 (14), 211 (31), 194 (24), 118 (57), 109 (21), 77
(33). (E)-(styryl)(4-methoxy-phenyl)sulfide (3h).8g Yield: 0.090 g (62%). 1H NMR
(CDCl3, 300 MHz) d = 7.43 (d, J = 8.2 Hz, 2H), 7.29–7.34 (m, 4H), 6.76–6.82 (m,
3H), 6.73 (d, J = 15.4 Hz, 1H), 6.41 (d, J = 15.4 Hz, 1H), 3.71 (s, 3H). 13C NMR
(CDCl3, 75 MHz) d = 136.7, 133.4, 132.9, 128.9, 128.6, 128.2, 127.1, 125.6,
125.7, 114.8, 55.3. MS m/z (rel int.,%) 242 (100), 241 (22), 211 (30), 194 (16),
165 (36), 91 (19), 77 (40). (E)-(styryl)(4-methyl-phenyl)sulfide (3i).8g Yield:
0.102 g (75%). 1H NMR (CDCl3, 300 MHz) d = 7.44–7.49 (m, 3H), 7.34–7.07 (m,
6H), 6.78 (d, J = 15.5 Hz, 1H), 6.57 (d, J = 15.5 Hz, 1H), 2.28 (s, 3H). 13C NMR
(CDCl3, 75 MHz) d = 137.3, 132.7, 130.6, 129.9, 128.7, 128.6, 128.3, 127.4,
125.9, 124.4, 21.0. MS m/z (rel int.,%) 226 (100), 225 (21), 211 (58), 178 (38), 91
(31), 77 (30). (E)-(styryl)(4-chloro-phenyl)sulfide (3j).8g Yield: 0.088 g (60%). 1H
NMR (CDCl3, 400 MHz) d = 7.58–7.52 (m, 4H), 7.44–7.27 (m, 9H), 6.85 (d,
J = 15.4 Hz, 1H), 6.76 (d, J = 15.4 Hz, 1H) 13C NMR (CDCl3,100 MHz) d = 140.5,
140.4, 135.2, 133.8, 132.9, 132.1, 130.9, 129.2, 128.7, 127.3, 126.8, 126.4, 122.5.
MS m/z (rel int.,%) 246 (100), 245 (25), 210 (27), 201 (30), 178 (64), 121 (27), 77
(54). (E)-(styryl)(phenyl)telluride (3k).19 Yield: 0.158 g (85%). 1H NMR (CDCl3,
400 MHz) d = 7.82–7.66 (m, 2H), 7.55 (d, J = 16.6 Hz, 1H), 7.37–7.18 (m, 8H),
7.10 (d, J = 16.6 Hz, 1H. 13C NMR (CDCl3, 100 MHz) d = 143.3, 138.0, 137.8,
129.5, 129.3, 128.6, 127.8, 127.7, 126.1, 101.5. MS m/z (rel int.,%) 310 (25), 308
(24), 207 (5), 180 (100), 103 (42), 77 (17). (E)-(4-methoxystyryl)(phenyl)telluride
(3l).20 Yield: 0.181 g (89%). 1H NMR (CDCl3, 400 MHz) d = 7.80–7.68 (m, 2H);
7.49 (d, J = 16.4 Hz, 1H); 7.29–7.15 (m, 7H); 7.12 (d, J = 16.6 Hz, 1H); 3.78 (s,
3H). 13C NMR (CDCl3, 100 MHz) d = 155.2, 148.6, 139.8, 137.4, 127.8, 127.5,
126.7, 126.3, 125.8, 113.4, 55.2. MS m/z (rel int.,%) 340 (10), 307 (23), 231 (32),
205 (100), 129 (28), 108 (16), 77 (42). (E)-(4-methylstyryl)(phenyl)telluride
(3m).8e Yield: 0.126 g (65%). 1H NMR (CDCl3, 300 MHz) d = 2.32 (s, 3H), 7.08–
Acknowledgments
The authors are grateful to FAPERGS and CNPq (PRONEX 10/
0005-1 and PRONEM 11/2026-4), CAPES, and FINEP for the finan-
cial support.
References and notes
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7.14 (m, 3H), 7.16–7.30 (m, 5H), 7.47 (d, J = 16.6 Hz, 1H), 7.67–7.70 (m, 2H). 13
C
NMR (CDCl3, 75 MHz) d = 21.2, 99.7, 113.7, 126.1, 127.8, 129.3, 129.5, 135.5,
137.6, 138.0, 143.8. MS m/z (rel int.,%) 324 (5), 284 (12), 207 (24), 194 (30), 154
(39), 115 (17), 77 (100). (E)-(4-chlorostyryl)(phenyl)telluride (3n).8e Yield:
0.148 g (72%). 1H NMR (CDCl3, 400 MHz) d = 6.98 (d, J = 16.4 Hz, 1H); 7.51 (d,
J = 16.4 Hz, 1H); 7.15–7.32 (m, 7H); 7.67–7.78 (m, 2H). 13C NMR (CDCl3,
100 MHz) d = 102.8, 113.1, 1 27.2, 128.1, 128.7, 129.5, 133.4, 136.5, 138.1,
141.1. MS m/z (rel int.,%) 343 (9), 276 (15), 234 (14), 206 (21), 188 (37), 135
(30), 112 (100), 77 (11). (E)-(2-methoxystyryl)(phenyl)telluride (3o). Yield:

3480
L. C. C. Gonçalves et al. / Tetrahedron Letters 54 (2013) 3475–3480
0.153 g (75%). 1H NMR (CDCl3, 300 MHz) d = 7.62–7.54 (m, 2H); 7.38–7.29 (m,
46, 8761; (c) Stefani, H. A.; Costa, I. M.; Zeni, G. Tetrahedron Lett. 1999, 40, 9215;
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A. Tetrahedron Lett. 2007, 48, 1485; (e) Diego, D. G.; Cunha, R. L. O. R.;
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A. A.; Comasseto, J. V. Tetrahedron Lett. 2010, 51, 6843; (g) Oliveira, R. A.;
Oliveira, J. M.; Rahmeier, L. H. S.; Comasseto, J. V.; Menezes, P. H. Tetrahedron
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6H); 7.19 (d, J = 16.6 Hz, 1H); 7.12 (d, J = 16.6 Hz, 1H); 3.76 (s, 3H). 13C NMR
(CDCl3, 100 MHz) d = 55.2, 103.4, 112.9, 113.2, 124.1, 127.9, 138.4, 138.7,
150.5, 150.9. MS m/z (rel int.,%) 342 (14), 340 (7), 234 (26), 209 (100), 207 (21),
160 (19), 116 (23), 109 (15), 77 (49). (Z)-(styryl)(phenyl)telluride (3p).8e Yield:
0.112 g (60%). 1H NMR (CDCl3, 200 MHz) d = 7.06 (d, J = 10.6 Hz, 1H); 7.43 (d,
J = 10.6 Hz, 1H); 7.13–7.37 (m, 8H); 7.70–7.75 (m, 2H). 13C NMR (CDCl3,
50 MHz) d = 109.2, 115.3, 127.3, 127.4, 128.0, 128.4, 129.3, 136.8, 137.9, 138.8.
MS m/z (rel int.,%) 310 (17), 306 (22), 231 (35), 204 (27), 173 (32), 107 (18), 77
(100). (Z)-(2-methoxystyryl)(phenyl)telluride (3q). Yield: 0.136 g (67%). 1H NMR
(CDCl3, 300 MHz) d = 7.59–7.53 (m, 3H); 7.36–7.25 (m, 6H); 7.21 (d, J = 10.6 Hz,
1H); 7.10 (d, J = 10.6 Hz, 1H); 3.80 (s, 3H). 13C NMR (CDCl3, 100 MHz) d = 55.17,
104.6, 110. 29, 114.23, 126.01, 127.89, 138.91, 141.55, 150.15, 158.97. MS m/z
(rel int.,%) 340 (7), 309 (21), 210 (100), 206 (11), 157 (17), 124 (33), 109 (18),
77 (21). (E)-(styryl)(4-methoxy-phenyl)telluride (3r).19 Yield: 0.153 g (75%). 1H
NMR (CDCl3, 300 MHz) d = 3.77 (s, 3H), 6.80 (d, J = 8.6 Hz, 2H), 6.94 (d,
J = 16.6 Hz, 1H), 7.24–7.29 (m, 5H), 7.48 (d, J = 16.6 Hz, 1H), 7.70 (d, J = 8.6 Hz,
2H). 13C NMR (CDCl3, 75 MHz) d = 55.1, 102.7, 110.2, 115.5, 126.0, 127.6, 128.5,
140.7, 140.8, 141.3, 160.0. MS m/z (rel int.,%) 340 (10), 214 (100), 199 (91), 171
(31), 128 (13), 107 (9), 77 (10).
16. Recycle of catalytic system: The aforementioned procedure14 was used with (E)-
b-bromostyrene 1a (0.6 mmol), diphenyl disulfide 2a (0.3 mmol), CuI
(5 mol %), zinc dust (0.6 mmol), and glycerol (1.5 mL). After the reaction was
complete (followed by TLC), the reaction mixture was washed with a mixture
of hexane/ethyl acetate (95:5) (3Â 3 mL) and the upper organic phases were
separated from the glycerol one. The product was isolated according to the
procedure above. The resulting glycerol phase was dried under vacuum and
reused for further reactions without previous purification, simply by adding
more reagents 1a and 2a.
17. Yang, Y.; Rioux, R. M. Chem. Commun. 2011, 6557.
18. Wang, Z.-L.; Tang, R.-Y.; Luo, P.-S.; Deng, C.-L.; Zhong, P.; Li, J.-H. Tetrahedron
2008, 64, 10670.
19. Braga, A. L.; Barcellos, T.; Paixão, M. W.; Deobald, A. M.; Godoi, M.; Stefani, H.
A.; Cella, R.; Sharma, A. Organometallics 2008, 27, 4009.
20. Silveira, C. C.; Braga, A. L.; Guadagnin, R. C. Tetrahedron Lett. 2003, 44, 5703.
15. For examples of vinyl tellurides as key intermediates in total organic synthesis,
see: (a) Oliveira, J. M.; Zeni, G.; Malvestiti, I.; Menezes, P. H. Tetrahedron Lett.
2006, 47, 8183; (b) Alves, D.; Nogueira, C. W.; Zeni, G. Tetrahedron Lett. 2005,