Selective synthesis of (Z)-chalcogenoenynes and (Z,Z)-1,4-bis-chalcogenbuta-1,3-dienes using PEG-400

Article abstract of DOI:10.5935/0103-5053.20160094

We present here our results on the temperature controlled, selective hydrochalcogenation of 1,4-diorganyl-1,3-butadiynes with nucleophilic species of selenium, tellurium and sulfur generated in situ from the respective diaryl dichalcogenide and NaBH₄

Full text of DOI:10.5935/0103-5053.20160094

http://dx.doi.org/10.5935/0103-5053.20160094
J. Braz. Chem. Soc., Vol. 27, No. 11, 2046-2054, 2016.
Printed in Brazil - ©2016 Sociedade Brasileira de Química
0
103 - 5053 $6.00+0.00
Article
Selective Synthesis of (Z)-Chalcogenoenynes and (Z,Z)-1,4-bis-Chalcogenbuta-1,3-
dienes Using PEG-400
Renata G. Lara, Liane K. Soares, Raquel G. Jacob, Ricardo F. Schumacher and
Gelson Perin*
Laboratório de Síntese Orgânica Limpa (LASOL), Centro de Ciências Químicas, Farmacêuticas e de
Alimentos (CCQFA), Universidade Federal de Pelotas (UFPel), CP 354, 96010-900 Pelotas-RS, Brazil
We present here our results on the temperature controlled, selective hydrochalcogenation of
1,4-diorganyl-1,3-butadiynes with nucleophilic species of selenium, tellurium and sulfur generated
in situ from the respective diaryl dichalcogenide and NaBH . Using polyethylene glycol (PEG)-400
4
o
o
at 30 C the (Z)-chalcogenoenynes are obtained and at 90 C the (Z,Z)-bis-chalcogen-1,3-butadienes
are produced in good to excellent yields. Alternatively to conventional oil bath heating, the use of
microwave irradiation is also presented as an alternative energy source that provides the expected
products in few minutes.
Keywords: organochalcogens, PEG-400, enyne, microwave irradiation, 1,3-butadienes
Introduction
since they are versatile intermediates for the selective
construction of isolated or conjugated olefins. One of
7
Enynes, dienes and related unsaturated structures are key
fragments found in a diverse array of natural products. A
widely studied example is the naturally occurring pheromone
the main advantages of using vinyl chalcogenides is the
fact that these species can be transmetalated with many
organometallic reagents to generate the corresponding
vinyl organometallics with retention of the double-bond
1
bombykol, isolated from the silkworm moth (Bombyx
2
8
mori), which was firstly characterized by Butenandt et al.
geometry. Still, among the broad scope of applications
over 40 years ago. Bombykol contains conjugated olefins
of E,Z-configuration and represents a milestone on the
structural elucidation of a natural compound important for
of vinyl chalcogenides, the importance for the synthesis
of enediynes, enynols and chalcogenophenes is well
documented in the literature.
9
8
10
3
chemical interactions between live organisms. Moreover,
On the other hand, the development of environmentally
benign and clean synthetic methods, including those
involving solvent-free or alternative solvents, such as
water, ionic liquids (ILs) and glycerol, has increased in
the last years and is the main topic of many books and
these unsaturated structures represent important moieties
4
found in a diverse array of biologically active compounds,
for example the drug lovastatin, an important 3-hydroxy-3-
methylglutaryl-coenzymeA (HMG-CoA) reductase inhibitor
and antihypercholesterolemic agent that has a diene portion
1
1
reviews. Alternatively, the use of polyethylene glycol
(PEG) has been shown as promising medium for organic
reactions that suppresses some drawbacks of conventional
5
in its structure.
The broad scope of applications for conjugated enynes
and dienes requires selective and efficient methods of
synthesis commonly involving transition metal catalyzed
11
solvents, and its application was previously described by
12
13
our group and others. Furthermore, compared to the use
of other hydroxylated solvents, such as ethanol or glycerol,
better results have been obtained in the synthesis of vinyl
6
cross-coupling reactions. Although these methods are
undeniably efficient, protocols using stable and easily
handled materials for rigorous regio- and stereochemical
controlled synthesis remains a challenge.
In this way, vinyl chalcogenides have been found to be
very useful tools in organic synthesis and materials science
12,14,15
chalcogenides using PEG-400.
In this sense, we describe herein our results on the
hydrochalcogenation of 1,4-diorganyl-1,3-butadiynes 1
under mild reaction conditions using diaryl dichalcogenides
2
and PEG-400 as solvent (Scheme 1). The selective product
*
e-mail: gelson_perin@ufpel.edu.br
formation 3 or 4 was obtained by a simple temperature

Vol. 27, No. 11, 2016
Lara et al.
2047
Scheme 1. General scheme of the present work.
controlled reaction. When the reaction was carried
out at 30 C, using conventional heating or microwave
When the reaction was held at room temperature under
magnetic stirring and inert atmosphere, a low yield of the
expected (Z)-1-phenylseleno-1,4-diphenylbut-1-en-3-yne
3a was observed, not exceeding 44% yield even after
o
(
MW) irradiation as the heating source, the mono-
hydrochalcogenated product 3 was obtained. In contrast,
o
o
at 90 C the uncommon 1,4-bis-chalcogenbutadiene 4 was
96 h (Table 1, entry 1). A mild reaction heating to 30 C
isolated.
for 24 h using a conventional oil bath was significant to
improve the reaction yield to 72% (Table 1, entry 2). We
believe this improvement is due to the higher solubility of
the reagents in PEG-400. However, the best performance
for this reaction was achieved when the amount of the
diphenyl diselenide 2a was increased from 0.5 to 1 eq,
corresponding to an excess of the phenylchalcogenium
anion (Table 1, entry 3).
Results and Discussion
Initially, we chose 1,4-diphenyl-1,3-butadiyne 1a
(
0.4 mmol) and diphenyl diselenide 2a (0.2 mmol) as
standard materials to optimize reaction conditions for the
synthesis of (Z)-chalcogenoenynes 3a using PEG-400 as
solvent and NaBH as reducing agent under N atmosphere.
The influence of solvent, temperature, stoichiometry and
two different heating sources, the conventional oil bath and
the focused microwave irradiation, were examined and the
results are presented in Table 1.
Hoping to increase the reaction yield and reduce the
4
2
o
reaction time, an experiment was carried out at 60 C and
surprisingly a mixture of products 3a and 4a was detected
1
after H nuclear magnetic resonance (NMR) analysis,
with a ratio of 56:44, respectively (Table 1, entry 4).
a
Table 1. Investigation of the best conditions for synthesis of 3a
o
b
entry
2a / eq
0.5
Solvent
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
glycerol
Temperature / C
time / h
96
Yield / %
3a:4a ratio
100:0
100:0
100:0
56:44
7:93
1
2
3
4
5
6
7
r.t.
30
44
72
81
0.5
24
1.0
30
24
c
1.0
60
24
78
c
1.0
90
6
51
1.0
90
12
n.r.
95
–
1.0
PEG-400
PEG-400
30 (MW)
90 (MW)
1.25
0.5
100:0
0:100
8
1.0
69
a
b
1
The reactions were performed using 1a (0.4 mmol), NaBH (2 eq to 2a) and solvent (3.0 mL) under N atmosphere; determined by H nuclear magnetic
4
2
c
resonance (NMR); yield is given for the mixture 3a + 4a. PEG: polyethylene glycol; r.t.: room temperature; n.r.: no reaction; MW: microwave.

2
048
Selective Synthesis of (Z)-Chalcogenoenynes and (Z,Z)-1,4-bis-Chalcogenbuta-1,3-dienes
J. Braz. Chem. Soc.
Relying on this result, we performed the reaction at a
higher temperature expecting to increase the formation of
the product 4a (Table 1, entry 5). Thus, the reaction was
carried out at 90 C, using 1.0 eq of the dichalcogenide 2a
in PEG-400 as solvent and the compound 4a was obtained
preferentially in 51% yield after 6 h.
3g was obtained in 97% yield after 6 h (Table 2, entry 7).
Under microwave irradiation, the reaction time reduced to
10 min and 3g was isolated in 98% yield.
o
Attracted by promising results in our recent studies
1
6
regarding of glycerol derivatives, we investigated the
possibility of using the diselenide glycerol derivative 2e in the
presence of diyne 1a (Table 2, entry 8). The reaction proceeds
smoothly, furnishing the unprecedented product 3h in 77%
yield after 24 h. The use of microwave irradiation was also
satisfactorily employed to generate the product 3h, which
was obtained in an almost quantitative yield after 10 min.
The use of chalcogen-substituted dienes as reagents
for the construction of more complex structures is well
Ethanol is the traditional solvent employed in
8
hydrochalcogenation reactions, however, our recent
findings have demonstrated the satisfactory use of glycerol
1
4
as an alternative. Based on this, glycerol was also tested
as solvent, but no products were detected (Table 1, entry 6).
In order to obtain an efficient protocol in terms of
energy economy, we chose to perform the reaction under
8
microwave irradiation. Thus, reacting the buta-1,3-diyne
documented in literature. On this basis of this and the
o
1
a with the diphenyl diselenide 2a at 30 C for 75 min,
results shown in entries 5 and 8 in Table 1, we undertook
a systematic study to generate a series of (Z,Z)-1,4-bis-
chalcogenbuta-1,3-dienes 4 employing 1,4-diphenyl-1,3-
butadiyne 1a or 2,7-dimethylocta-3,5-diyne-2,7-diol 1b
and different diorganyl dichalcogenides 2a-d (Table 3).
When the 1,3-butadiyne 1a was reacted with the diphenyl
resulted in all starting materials being completely consumed
and the desired product 3a was obtained in excellent
yield and selectivity (Table 1, entry 7). When the reaction
o
was performed at 90 C under microwave irradiation, the
product 4a was detected after only 0.5 h in 69% yield
without the formation of 3a as byproduct (Table 1, entry 8).
With the optimized reaction conditions for the
synthesis of the organochalcogenoenyne 3 in hand, using
conventional heating (method A) (Table 1, entry 3) or
microwave irradiation (method B) (Table 1, entry 7), we
envisioned extending these protocols to different diaryl
o
diselenide 2a at 90 C, the 1,4-bis-phenylseleno-1,3-diene
4a was obtained in 51% yield under conventional heating
after 24 h. However, using MW irradiation allowed a yield
increase to 69% and a reaction time decrease to 30 min.
It is important to mention that the (Z,Z)-configuration
was obtained for both heating methods (Table 3, entry 1).
Similarly, the synthesis of (Z,Z)-1,4-bis-phenylthiobuta-
1,3-diene 4b is also demonstrated in entry 2. In this
case, the diphenyl disulfide 2b was employed, giving the
corresponding diene 4b in 65 and 69% yield for methods A
o
dichalcogenides 2a-e and diynes 1a-b at 30 C (Table 2).
In regards to product stereochemistry, the formation of
(
Z)-enynes was preferential for all the tested examples,
1
5
which complies with the literature. Thus, (Z)-3a was
obtained exclusively for the reaction of 1,4-diphenyl-1,3-
butadiyne 1a with diphenyl diselenide 2a and in excellent
yields (Table 2, entry 1). When diphenyl disulfide 2b
was tested, a similar stereoselectivity was observed and
the (Z)-thioenyne 3b was obtained in 82% yield after
o
and B, respectively, at 90 C. Using the dibutyl diselenide 2d
in the presence of 1a, the desired product 4c was obtained
in 71% yield using conventional oil bath and 64% yield
o
by microwave irradiation even at 30 C (Table 3, entry 3).
We believe that the more pronounced nucleophilicity of
the dibutyl diselenide 2d relative to diphenyl diselenide 2a
contributed to the good yield of 4c, which was also observed
for 3g. When the 2,7-dimethylocta-3,5-diyne-2,7-diol 1b
was reacted with diphenyl diselenide 2a, the product 4d
was isolated in 69 and 73% yield by the method A and B,
respectively (Table 3, entry 4). Finally, the diyne 1a and the
diphenyl ditelluride 2c were employed to react under the
same reaction conditions (Table 3, entry 5). However, the
product (Z,Z)-1,4-bis-phenyltellurobuta-1,3-diene 4e was
not observed. Instead, a complex mixture of compounds
was obtained.
2
4 h (Table 2, entry 2). The alternative MW irradiation
also gave the corresponding product 3b in 96% after
5 min. Diphenyl ditelluride 2c was also used as the
7
starting material to react with the 1,3-butadiyne 1a and
furnished the corresponding 1-phenyltelluro-1-en-3-yne
3
c preferentially in (Z)-configuration (Table 2, entry 3). In
order to increase the screening of (Z)-enyne compounds, we
next turned our attention to reactions of 2,7-dimethylocta-
3,5-diyne-2,7-diol 1b with the diaryl dichalcogenides 2a-c
(
(
Table 2, entries 4-6). A closer inspection shows that the
Z)-configuration was obtained for all formed products 3d-f
rather than (E). Furthermore, the products were obtained in
good to excellent yields for both methods A and B, while
the reaction times required for method B, MW irradiation,
were much shorter. Interestingly, when 1b was reacted with
dibutyl diselenide 2d, the expected (Z)-butylselenoenyne
At same time we were preparing our manuscript,
Venkateswarlu and Chandrasekaran reported the mono- or
bis-chalcogenation of buta-1,3-diynes using rongalite and
17
potassium carbonate in N,N-dimethylformamide (DMF):H O
2
as solvent. Despite a satisfactory procedure to produce (Z)-

Vol. 27, No. 11, 2016
Lara et al.
2049
o
a
Table 2. Synthesis of chalcogenoenynes 3a-h using NaBH and PEG-400 at 30 C
4
b
entry
Diyne 1
(ArY) 2
Product 3
Yield / % (method)
2
(
C H Se)
81 (A)
95 (B)
6
5
2
1
2
a
1
a
3
a
(
C H S)
82 (A)
96 (B)
6
5
2
2
1a
1a
2
b
3
b
(
C H Te)
61 (A)
77 (B)
c
6
5
2
3
2
c
3
c
7
0 (A)
4
5
6
2a
2b
2c
d
6
9 (B)
1
b
3
d
9
9 (A)
1b
1b
d
8
1 (B)
3
e
5
1 (A)
d
5
0 (B)
3
f
e
f
(
C H Se)
97 (A)
98 (B)
4
9
2
7
1b
2
d
3
g
7
7 (A)
8
1a
f
9
8 (B)
2
e
3
h
a
b
The reactions were performed using diyne 1 (0.4 mmol), diaryl dichalcogenide 2 (0.4 mmol), NaBH (0.8 mmol) and PEG-400 (3.0 mL) under N ; method
4
2
o
o
c
A: conventional heating at 30 C during 24 h; method B: MW irradiation at 30 C during 1.25 h; ratio of Z:E isomers determined by gas chromatography-
mass spectrometry (GC-MS): 93:7; reaction time: 2 h; reaction time: 6 h; reaction time: 10 min.
d
e
f

2
050
Selective Synthesis of (Z)-Chalcogenoenynes and (Z,Z)-1,4-bis-Chalcogenbuta-1,3-dienes
J. Braz. Chem. Soc.
a
Table 3. Synthesis of bis-chalcogen-1,3-butadienes 4a-d using NaBH and PEG-400
4
o
b
entry
(ArY) 2
Temperature / C
Products 4
Yield / % (method)
2
(
C H Se)
51 (A)
69 (B)
c
6
5
2
1
90
2
a
4
a
(
C H S)
65 (A)
69 (B)
c
6
5
2
2
90
30
90
2
b
4
b
(
C H Se)
71 (A)
64 (B)
4
9
2
3
2
d
4
c
6
7
9 (A)
3 (B)
d
4
2a
4
d
5
2c
90
–
4
e
a
The reactions were performed using the diyne 1a (0.4 mmol), diaryl dichalcogenide 2 (0.4 mmol), NaBH (0.8 mmol) and PEG-400 (3.0 mL) under N ;
method A: conventional heating during 6 h; method B: MW irradiation during 30 min; 3-5% of the corresponding (Z)-enyne was isolated; the reaction
4
2
b
c
d
was performed using the 2,7-dimethylocta-3,5-diyne-2,7-diol 1b.
chalcogenenynes, lower reaction yields and poor selectivity
were observed when buta-1,3-dienes were synthesized. In
contrast, we developed an efficient and selective method
to synthesize (Z,Z)-1,4-bis-organylchalcogen-1,3-dienes 4
in good yields using conventional heating or microwave
irradiation to promote the reaction in an environmentally
benign solvent.
1,3-butadiynes under mild reaction conditions using
PEG-400 as solvent. This study is relevant because under
similar reaction conditions, by choosing the temperature,
o
a selective product formation can be controlled. At 30 C
the (Z)-chalcogenoenynes are obtained and increasing
o
the temperature to 90 C the (Z,Z)-1,4-bis-chalcogen-
1,3-butadienes are produced in good to excellent yields.
Alternatively to the conventional method using oil bath
heating, the results for the use of microwave irradiation
under the same reaction conditions are also presented as an
alternative heating source that provide the expected products
in few minutes. In general, aliphatic dichalcogenides
Conclusions
We developed an alternative and stereoselective
method for the hydrochalcogenation of conjugated

Vol. 27, No. 11, 2016
Lara et al.
2051
were more reactive than arylic chalcogenides, specially
dibutyl diselenide due to high nucleophilicity, and the
corresponding enynes and dienes were obtained in higher
yields. The use of PEG as a non-toxic solvent opens new
possibilities for future applications of this in green and
sustainable chemistry.
at room temperature under stirring. Then, the mixture
was heated slowly to 30 C and the reaction progress
was followed by TLC. After 24 h, water (3.0 mL) was
added and the mixture was extracted with ethyl acetate
(3 × 5.0 mL). The organic layers were combined, washed
o
with brine solution (3.0 mL) and dried with MgSO . The
4
solvent was removed under vacuum and the product was
isolated by column chromatography using hexane/ethyl
acetate as eluent.
Experimental
Materials and methods
Method B: in a 10 mL glass vial equipped with a small
magnetic stirring bar, containing a solution of diyne 1
(0.4 mmol) and diphenyl dichalogenide 2 (0.4 mmol)
in PEG-400 (2.0 mL) under N atmosphere, NaBH
1
Proton nuclear magnetic resonance ( H NMR)
spectra were obtained at 300 MHz on Varian Inova 300
and at 400 MHz on Bruker DPX spectrometers. Spectra
2
4
(0.8 mmol) was added at room temperature. The mixture
was then irradiated in a focused microwaves reactor (CEM)
were recorded in CDCl solutions. Chemical shifts are
3
o
reported in ppm, referenced to tetramethylsilane (TMS)
as the external reference. Data are reported as follows:
chemical shift (d), multiplicity, integrated intensity and
coupling constant (J) in Hz. C NMR spectra were
obtained at 75 MHz on Varian Inova 300 and at 100 MHz
on Bruker DPX spectrometers. Spectra were recorded in
at 30 C, using an irradiation maximum power of 50 W.
After stirring for 10-120 min the products were isolated
as described above for method A. All the compounds were
characterized and spectral data are listed below.
1
3
1
5
(Z)-1-Phenylselanyl-1,4-diphenylbut-1-en-3-yne (3a)
CDCl solutions. Chemical shifts are reported in ppm,
Yield: 0.117 g (81%, method A), 0.136 g (95%,
method B); yellow solid; m.p. 67-70 C; H NMR
3
o
1
referenced to the solvent peak of CDCl . Low-resolution
3
mass spectra (MS) were obtained with a Shimadzu gas
chromatograph-mass spectrometer (GC-MS)-QP2010.
High-resolution MS (HRMS) were obtained on an
LTQ Orbitrap Discovery mass spectrometer (Thermo
Fisher Scientific). This hybrid system has a LTQ XL
linear ion trap mass spectrometer and an Orbitrap mass
analyzer. The experiments were performed via direct
(400 MHz, CDCl ) d 7.41-7.46 (m, 4H), 7.31-7.34 (m, 2H),
3
7.27-7.29 (m, 3H), 7.15-7.16 (m, 3H), 7.05-7.06 (m, 3H),
13
6.40 (s, 1H); C NMR (100 MHz, CDCl ) d 147.1, 139.5,
3
133.1, 131.5, 130.0, 128.7, 128.35, 128.33, 128.31, 128.2,
+
128.1, 126.9, 123.3, 112.7, 97.7, 88.3; MS 360 ([M ], 18.9),
279 (23.0), 202 (100.0), 77 (12.6).
-
1
infusion (DI) of sample (flow: 10 μL min ) in the
positive-ion mode using electrospray ionization (ESI).
Elemental composition calculations for comparison were
executed using the specific tool included in the Qual
Browser module of Xcalibur (Thermo Fisher Scientific,
release 2.0.7) software. Column chromatography was
performed using Merck silica gel (230-400 mesh).
Thin layer chromatography (TLC) was performed
(Z)-1-Phenylthio-1,4-diphenylbut-1-en-3-yne (3b)
Yield: 0.102 g (82%, method A), 0.120 g (96%,
1
method B); yellow solid; m.p. 94-95 ºC; H NMR
(400 MHz, CDCl ) d 7.50-7.53 (m, 2H), 7.43-7.46 (m, 2H),
3
7.27-7.29 (m, 3H), 7.19-7.24 (m, 4H), 7.03-7.15 (m, 4H),
13
6.32 (s, 1H); C NMR (100 MHz, CDCl ) d 147.1, 138.2,
3
134.4, 131.5, 130.3, 128.6, 128.3, 128.2, 127.9, 126.3,
+
123.2, 112.2, 98.3, 87.6; MS 312 ([M ], 93.7), 279 (12.1),
®
using DC-Fertigfolien ALUGRAM Xtra SIL G/UV ,
202 (100.0), 77 (13.7); ESI-HRMS calcd. for C H S
2
54
22 16
+
0
.20 mm thickness. For visualization, TLC plates were
[M + H] : 313.1051; found: 313.1025.
either placed under UV light, stained with iodine vapor, or
acidic vanillin. All solvents were used as purchased unless
otherwise noted. PEG-400 was obtained fromAldrich and
used without further purification.
(Z)-1-Phenyltellanyl-1,4-diphenylbut-1-en-3-yne (3c)
Yield: 0.100 g (61%, method A), 0.126 g (77%,
1
method B); dark yellow solid; m.p. 62-66 ºC; H NMR
(
400 MHz, CDCl ) d 7.50-7.52 (m, 4H), 7.26-7.33 (m,
3
Generalprocedureforthesynthesisof(Z)-chalcogenoenynes
5H), 7.09-7.13 (m, 4H), 6.97-7.01 (m, 2H), 6.46 (s, 1H);
13
3
a-h
C NMR (100 MHz, CDCl ) d 141.3, 139.3, 139.0, 131.4,
3
1
28.9, 128.6, 128.4, 128.3, 127.84, 127.80, 127.7, 123.1,
+
Method A: to a mixture of diyne 1 (0.4 mmol) and
116.1, 114.7, 97.3, 90.1; MS 410 ([M ], 15.4), 279 (17.6),
202 (100.0), 77 (13.7); ESI-HRMS calcd. for C H Te
[M + H] : 411.0392; found: 411.0369.
diphenyl dichalcogenide 2 (0.4 mmol) in PEG-400 (3.0 mL)
under N atmosphere, NaBH (0.8 mmol) was added
2
2
16
+
2
4

2
052
Selective Synthesis of (Z)-Chalcogenoenynes and (Z,Z)-1,4-bis-Chalcogenbuta-1,3-dienes
J. Braz. Chem. Soc.
(
(
Z)-2,7-Dimethyl-3-(phenylselanyl)oct-3-en-5-yne-2,7-diol
2.86 (dd, 1H, J 12.3 and 5.1 Hz), 2.65 (dd, 1H, J 12.3 and
8.0 Hz), 1.35 (s, 3H), 1.29 (s, 3H); C NMR (75 MHz,
15
13
3d)
Yield: 0.111 g (70%, method A), 0.109 g (69%,
method B); light yellow solid; m.p. 103-106 ºC; H NMR
CDCl ) d 146.2, 139.5, 131.4, 128.8, 128.6, 128.33, 128.31,
3
1
128.2, 123.3, 112.3, 109.5, 97.2, 88.2, 75.5, 69.1, 28.9, 26.9,
+
(
400 MHz, CDCl ) d 7.42-7.45 (m, 2H), 7.18-7.28 (m,
25.7.; MS 398 ([M ], 24.9), 298 (1.1), 282 (20.1), 202 (87.5),
3
3
6
1
3
H), 6.50 (s, 1H), 2.32 (br s, 1H), 1.72 (br s, 1H), 1.51 (s,
101 (41.3), 43 (100.0); ESI-HRMS calcd. for C H O Se
[M + H] : 399.0863; found: 399.0851.
22
22
2
1
3
+
H), 1.27 (s, 6H); C NMR (100 MHz, CDCl ) d 153.4,
3
31.9, 130.4, 129.0, 126.3, 114.4, 102.4, 80.1, 74.8, 65.3,
+
0.7, 29.1; MS 324 ([M ], 10.4), 306 (6.1), 167 (10.4), 77
General procedure for the synthesis of buta-1,3-dienes 4a-d
(
15.6), 43 (100.0).
Same procedure for (Z)-chalcogenoenynes using
o
(
Z)-2,7-Dimethyl-3-(phenylthio)oct-3-en-5-yne-2,7-diol
heating at 30-90 C during 6 h or 30 min (MW). All
1
8
(3e)
compounds were characterized and spectral data are listed
below.
Yield: 0.109 g (99%, method A), 0.089 g (81%,
1
method B); light yellow solid; m.p. 101-104 ºC; H NMR
(
400 MHz, CDCl ) d 7.26-7.34 (m, 4H), 7.14-7.18 (m,
(1Z,3Z)-1,4-Diphenyl-1,4-bis(phenylselanyl)buta-1,3-diene
3
17
1
6
1
3
H), 6.41 (s, 1H), 2.41 (brs, 1H), 1,77 (br s, 1H), 1.50 (s,
(4a)
1
3
H), 1.24 (s, 6H); C NMR (100 MHz, CDCl ) d 153.3,
After removal of the residual diphenyl diselenide 1a by
column chromatography, the product 4a was purified by
recrystallization in hexane.Yield: 0.106 g (51%, methodA),
3
36.0, 128.8, 128.2, 125.7, 113.0, 104.0, 79.3, 74.5, 65.3,
+
0.6, 28.9; MS 276 ([M ], 9.4), 258 (17.3), 200 (9.9), 77
o
(
11.8), 43 (100.0).
0.143 g (69%, method B); yellow solid; m.p. 134-138 C;
1
H NMR (400 MHz, CDCl ) d 7.61 (s, 2H), 7.56 (d, 4H,
3
(
(
Z)-2,7-Dimethyl-3-(phenyltellanyl)oct-3-en-5-yne-2,7-diol
J 6.7 Hz), 7.28-7.30 (m, 4H), 7.18-7.24 (m, 6H), 7.10-7.12
1
3
3f)
(m, 6H); C NMR (100 MHz, CDCl ) d 141.1, 138.3,
3
Yield: 0.076 g (51%, methodA), 0.074 g (50%, method
B); light yellow solid; m.p. 97-98 C; H NMR (300 MHz,
135.6, 131.2, 131.1, 129.0, 128.4, 128.2, 128.1, 126.4; DI-
o
1
+
MS 518 ([M ], 1.3), 361 (100.0), 280 (99.4), 202 (96.0), 77
+
CDCl ) d 7.63-7.67 (m, 2H), 7.18-7.26 (m, 3H), 6.52 (s,
(31.0); DI-HRMS calcd. for C H Se [M – H] : 516.9974;
3
28 22
2
1
6
1
3
4
3
H), 2.22 (br s, 1H), 1.70 (br s, 1H), 1.51 (s, 6H), 1.30 (s,
found: 516.9975.
1
3
H); C NMR (75 MHz, CDCl ) d 147.4, 136.3, 129.3,
3
27.2, 117.9, 115.8, 101.6, 82.4, 75.7, 65.3, 30.7, 29.7; MS
(1Z,3Z)-1,4-Diphenyl-1,4-bis(phenylthio)buta-1,3-diene
+
17
04 ([M ], 9.3), 286 (4.5), 246 (0.5), 167 (4.4), 59 (24.5),
(4b)
+
3 (100.0); ESI-HRMS calcd. for C H O Te [M + H] :
Yield: 0.109 g (65%, methodA), 0.117 g (69%, method
B); yellow solid; m.p. 192-196 ºC; H NMR (400 MHz,
16
20
2
1
75.0604; found: 375.0590.
CDCl ) d 7.76 (s, 2H), 7.63 (d, 4H, J 7.3 Hz), 7.12-7.25
3
1
3
(
(
Z)-2,7-Dimethyl-3-(butylselanyl)oct-3-en-5-yne-2,7-diol
(m, 14H), 7.05 (t, 2H, J 7.1 Hz); C NMR (100 MHz,
19
3g)
CDCl ) d 139.6, 138.1, 135.6, 133.4, 128.8, 128.7, 128.3
(overlapped 2 signals), 127.9, 125.8; MS 422 ([M ], 5.8),
313 (100.0), 235 (23.1), 202 (20.6), 77 (5.9).
3
+
Yield: 0.118 g (97%, methodA), 0.119 g (98%, method
1
B); yellow oil; H NMR (300 MHz, CDCl ) d 6.36 (s, 1H),
3
3
1
0
1
1
7
.04 (t, 2H, J 7.5 Hz), 2.73 (br s, 1H), 2.56 (br s, 1H), 1.62-
.72 (m, 2H), 1.57 (s, 6H), 1.43 (s, 6H), 1.36-1.48 (m, 2H),
(1Z,3Z)-1,4-Bis(butylselanyl)-1,4-diphenylbuta-1,3-diene
(4c)
13
.92 (t, 3H, J 7.3 Hz); C NMR (75 MHz, CDCl ) d 154.3,
3
12.2, 100.8, 80.1, 74.6, 65.5, 32.3, 31.2, 29.0, 28.2, 23.0,
Yield: 0.136 g (71%, method A), 0.122 g (64%,
+
o
1
3.6; MS 374 ([M ], 11.1), 356 (1.7), 224 (21.8), 207 (4.6),
method B); yellow solid; m.p. 62-64 C; H NMR
7 (33.4), 43 (100.0).
(300 MHz, CDCl ) d 7.60-7.63 (m, 4H), 7.29-7.39 (m,
3
6
H), 7.25 (s, 2H), 2.45 (t, 4H, J 7.4 Hz), 1.48 (quint, 4H,
(
Z)-2,2-Dimethyl-1,3-dioxolanylmethyl(1,4-diphenylbut-1-
J 7.4 Hz), 1.25 (sext, 4H, J 7.4 Hz), 0.77 (t, 6H, J 7.4 Hz);
13
en-3-yn-1-yl)selane (3h)
C NMR (75 MHz, CDCl ) d 141.4, 138.3, 133.6, 128.5,
3
+
Yield: 0.123 g (77%, method A), 0.157 g (98%, method
128.3, 127.8, 32.5, 26.5, 22.7, 13.5; MS 478 ([M ], 4.1), 341
(100.0), 285 (84.4), 204 (92.6), 102 (23.7), 77 (10.5), 57
1
B); yellow oil; H NMR (300 MHz, CDCl ) d 7.48-7.53 (m,
4
3
+
H), 7.32-7.40 (m, 6H), 6.25 (s, 1H), 4.12-4.18 (m, 1H), 4.07
(64.5), 41 (85.4); DI-HRMS calcd. for C H Se [M + H] :
24
30
2
(dd, 1H, J 8.2 and 5.9 Hz), 3.66 (dd, 1H, J 8.2 and 6.3 Hz),
479.0756; found: 479.0721.

Vol. 27, No. 11, 2016
Lara et al.
2053
(
3Z,5Z)-2,7-Dimethyl-3,6-bis(phenylselanyl)-octa-3,5-diene-
S.; Panatieri, R. B.; Braga, A. L.; Chem. Rev. 2006, 106, 1032;
Perin, G.; Lenardão, E. J.; Jacob, R. G.; Panatieri, R. B.; Chem.
Rev. 2009, 109, 1277; Zyk, N. V.; Beloglazkina, E. K.; Belova,
M.A.; Dubinina, N. S.; Russ. Chem. Rev. 2003, 72, 769; Kondo,
T.; Mitsudo, T.; Chem. Rev. 2000, 100, 3205; Gavrilova, G. M.;
Amosova, S. V.; Heteroat. Chem. 2006, 17, 491; Beletskaya, I.
P.; Ananikov, V. P.; Eur. J. Org. Chem. 2007, 3431.
1
7
2
,7-diol (4d)
Yield: 0.133 g (69%, methodA), 0.141 g (73%, method
o
1
B); yellow solid; m.p. 147-150 C; H NMR (400 MHz,
CDCl ) d 7.28-7.30 (m, 4H), 7.18-7.25 (m, 6H), 7.02 (s,
2
CDCl ) d 147.6, 132.4, 131.8, 130.5, 129.1, 126.4, 74.6,
2
(
3
13
H), 2.12 (br s, 2H), 1.29 (s, 12H); C NMR (100 MHz,
3
+
9.1; MS 464 ([M – 18] , 1.1), 325 (21.7), 249 (34.1), 59
8. Wirth, T.; Organoselenium Chemistry: Synthesis and Reactions;
Wiley-VCH: Weinheim, 2011; Schneider, C. C.; Caldeira, H.;
Gay, B. M.; Back, D. F.; Zeni, G.; Org. Lett. 2010, 12, 936;
Marino, J. P.; McLure, M. S.; Holub, D. P.; Comasseto, J. V.;
Tucci, F. C.; J. Am. Chem. Soc. 2002, 124, 1664; Tucci, F. C.;
Chieffi,A.; Comasseto, J.V.; Marino, J. P.; J. Org. Chem. 1996,
61, 4975; Lenardão, E. J.; Cella, R.; Jacob, R. G.; Silva, T. B.;
Perin, G.; J. Braz. Chem. Soc. 2006, 17, 1031; Dabdoub, M.
J.; Dabdoub, V. B.; Baroni, A. C. M.; Hurtado, G. R.; Barbosa,
S. L.; Tetrahedron Lett. 2010, 51, 1666.
100.0), 43 (77.7).
Supplementary Information
Supplementary data are available free of charge at
http://jbcs.sbq.org.br as PDF file.
Acknowledgments
The authors are grateful to CNPq, FAPERGS, CAPES
and FINEP for the financial support.
9. Alves, D.; Nogueira, C. W.; Zeni, G.; Tetrahedron Lett. 2005, 46,
8761; Oliveira, J. M.; Zeni, G.; Malvestiti, I.; Menezes, P. H.;
Tetrahedron Lett. 2006, 47, 8183; Braga, A. L.; Lüdtke, D. S.;
Vargas, F.; Donato, R. K.; Silveira, C. C.; Stefani, H. A.; Zeni,
G.; Tetrahedron Lett. 2003, 44, 1779; Raminelli, C.; Gargalaka
Jr., J.; Silveira, C. C.; Comasseto, J. V.; Tetrahedron Lett. 2004,
45, 4927; Fiandanese, V.; Marchese, G.; Naso, F.; Ronzini, L.;
Rotunno, D.; Tetrahedron Lett. 1989, 30, 243.
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