Stereoselective synthesis of alkynyl vinyl chalcogenides via horner-wittig reaction

Article abstract of DOI:10.1055/s-0028-1083322

New (diphenylphosphoryl)methyl phenylethynyl sulfides, selenides, or tellurides were prepared by the reaction of (diphenylphosphoryl)methyl p-toluenesulfonate with alkynethiols,-selenols, or-tellurols at room temperature. The (diphenylphosphoryl)methyl ph

Full text of DOI:10.1055/s-0028-1083322

PAPER
469
Stereoselective Synthesis of Alkynyl Vinyl Chalcogenides via Horner–Wittig
Reaction
Stereoselective
Sy
nthesi
a
s
of Alkyny
u
l
V
inyl
C
ha
d
lcogenides io C. Silveira,* Francieli Rinaldi, Rafael C. Guadagnin, Antonio L. Braga
Departamento de Química, Universidade Federal de Santa Maria, 97105-900, Santa Maria, RS, Brazil
Fax +55(55)32208754; E-mail: silveira@quimica.ufsm.br
Received 4 September 2008; revised 2 October 2008
ed into sulfur, selenium, or nitrogen heterocycles by reac-
Abstract: New (diphenylphosphoryl)methyl phenylethynyl sul-
fides, selenides, or tellurides were prepared by the reaction of
(diphenylphosphoryl)methyl p-toluenesulfonate with alkynethiols,
-selenols, or -tellurols at room temperature. The (diphenylphospho-
ryl)methyl phenylethynyl sulfides, selenides, or tellurides reacted
with aldehydes and cyclic ketones to give the corresponding alkynyl
vinyl sulfides, selenides, or tellurides, with preferential E-stere-
ochemistry, in a Horner–Wittig-type reaction.
tion with sodium sulfide, sodium selenide, or
methylamine.14 Alkynyl vinyl sulfides were also claimed
to have pesticide and bactericide activity.15
In light of the above comments and from our continuous
interest in the development of new vinyl chalcogenides
based on Horner–Wittig reaction,16 we became interested
in the development of practical stereoselective synthetic
methods for alkynyl vinyl chalcogenides. For instance, we
have recently described a detailed study of the synthesis
of symmetrical and unsymmetrical divinyl sulfides, se-
lenides, and tellurides from chalcogenyl phosphonates
and phosphine oxides, by reaction with arylaldehydes and
cyclic ketones.17 Thus, as a continuation of this study, we
planned the preparation of alkynyl vinyl sulfides, se-
lenides, and tellurides by a similar route, starting from
(diphenylphosphoryl)methyl phenylethynyl chalco-
genides 2a–c. The alkynylphosphine oxides 2a–c were
prepared in 68–89% isolated yield by the reaction of phe-
nylacetylene with butyllithium at 0 °C, followed by addi-
tion of elemental sulfur, selenium, or tellurium to the
lithium acetylide and (diphenylphosphoryl)methyl p-tolu-
enesulfonate (1) (Scheme 1). The compounds 2a–c can be
easily purified by column chromatography and are quite
stable compounds. The Horner–Wittig reaction of 2a–c
was subsequently performed, initially by reaction of the
sulfur derivative 2a with benzaldehyde in tetrahydrofuran
at 0 °C and using sodium hydride as the base; the corre-
sponding product 3a was obtained in 70% yield after one
hour of reaction (TLC monitoring). Next, a detailed study
was performed with aldehydes and ketones and the reac-
tion was showed to be effective also with selenium and
tellurium derivatives. The corresponding alkynyl vinyl
chalcogenides 3–5 were isolated in good yields (Table 1),
the only exception was the reaction of tellurium derivative
2c with isobutyraldehyde (entry 21).
Key words: Wittig reaction, alkynyl vinyl chalcogenides, vinyl
chalcogenides, chalcogenium, olefination
Organochalcogenium compounds have become the key
component of a variety of versatile and useful reagents for
organic synthesis. The multiple applications of organo-
chalcogenium chemistry have been well described in a
number of review articles1 and books.2 Functionalized
alkynyl3 and alkenyl4 chalcogenides have a great potential
in organic synthesis, since they are valuable intermediates
for the selective preparation of several organic com-
pounds. Furthermore, methods for the synthesis of chalco-
geno-substituted acetylenes have also been described in
recent years,3,5 although in a reduced number compared to
their vinylic counterparts. The most common approach to
alkynyl chalcogenides employs the reaction of a metal
alkynide with elemental chalcogenium followed by reac-
tion with an alkyl halide or an appropriate electrophilic re-
agent.5a
Among the many applications of vinyl selenides, divinyl
selenides, and vinyl sulfides, the cross-coupling reaction
with Grignard reagents catalyzed by nickel6 and
palladium7 to give the corresponding cross-coupled prod-
ucts, has been described. On the other hand, palladium-4a,8
and nickel-catalyzed6a,9 cross–coupling reactions and tel-
lurium–metal exchange reactions10 demonstrate the use-
fulness of vinyl tellurides.
Except for alkynyl vinyl sulfides, alkynyl vinyl chalco-
genides constitute a nearly unexplored class of unsaturat-
ed chalcogenides.11–13 Their preparation include multistep
sequences employing aldehydes or 2-chloroethyl
thiocyanate13 and the reaction of lithium acetylides with
b-chlorovinyl sulfenamides.11 The sulfur derivatives, as
the corresponding sulfoxides and sulfones, were convert-
1. Yº
Ph2P(O)
Ph
Li
Y
Ph
2. Ph2P(O)CH2OTs
2a–c
1
NaH, THF
R1R2CO
R1
R2
Y
Ph
Y = S, 3a–h
Y = Se, 4a–h
Y = Te, 5a–e
SYNTHESIS 2009, No. 3, pp 0469–0473
x
x
.
x
x
.2
0
0
9
Advanced online publication: 09.01.2009
DOI: 10.1055/s-0028-1083322; Art ID: M04908SS
Scheme 1
© Georg Thieme Verlag Stuttgart · New York

470
C. C. Silveira et al.
PAPER
Table 1 Alkynyl Vinyl Chalcogenides Prepared
Entry
1
R1
R2
H
H
H
H
H
H
Y
Compound
3a
Ratioa E/Z
11:1
12:1
11:1
9:1
Time (min)
60
Yield (%)
70
Ph
S
2
4-MeOC6H4
4-MeC6H4
4-ClC6H4
i-Pr
S
3b
3c
80
78
3
S
70
77
4
S
3d
3e
60
72
5
S
1:2
40
62
6
Pr
S
3f
2:1
40
60
7
(CH2)2CH(t-Bu)(CH2)2
S
3g
–
80
65b
59b
80
8
Ph
Ph
H
H
H
H
H
H
S
3h
4a
–
140
60
9
Ph
Se
Se
Se
Se
Se
Se
Se
Se
Te
Te
Te
Te
Te
9:1
10
11
12
13
14
15
16
17
18
19
20
21
4-MeOC6H4
4-MeC6H4
4-ClC6H4
i-Pr
4b
4c
16:1
12:1
9:1
80
83
70
81
4d
4e
60
83
1:2.5
1:2
40
77
Pr
4f
40
76
(CH2)2CH(t-Bu)(CH2)2
4g
–
80
70b
64b
58
Ph
Ph
H
H
H
H
H
4h
5a
–
140
80
Ph
9:1
4-MeOC6H4
4-MeC6H4
4-ClC6H4
i-Pr
5b
5c
12:1
11:1
9:1
100
90
64
60
5d
5e
70
60
1:2
40
26
a Determined by GC and 1H NMR.
b HMPA was used as a co-solvent (1 mL/mmol).
Concerning stereochemistry of the reaction, a very high the reaction of (diphenylphosphoryl)methyl phenylethy-
preference for the E-isomer could be detected by GC and nyl chalcogenides with ketones and aromatic and aliphatic
1H NMR from the reactions with aromatic aldehydes. This aldehydes by a Horner–Wittig route.
result could be expected from the known behavior of the
Horner–Wittig reaction of the diphenylphosphoryl group
The product ratios were analyzed by gas chromatography using a
in stabilized ylides.18 However, aliphatic aldehydes fur-
Shimadzu 14A gas chromatograph, capillary column, equipped
nished lower yields with a small preference for the Z-iso-
mer, based on the coupling constant values for the vinylic
hydrogen.
with an FID. IR data were collected on a Bruker FT Tensor 27 spec-
trophotometer. NMR spectroscopy was performed on Bruker 200
MHz and 400 MHz spectrometers, with TMS and CDCl3 as internal
standards. Melting points were obtained on a Microquimica
MQAPF-301 melting point apparatus. Mass spectrometry was car-
ried out on a Shimadzu QP2010 Plus instrument. Elemental analy-
When the reaction was performed with 4-tert-butylcyclo-
hexanone and benzophenone, good yields of the corre-
sponding trisubstituted alkynyl vinyl chalcogenides were ses were obtained from Central Analitica, Instituto de Química,
Universidade de São Paulo. All new compounds were adequately
characterized; detailed data for representative compounds are given
below.
obtained with 2a and 2b (Table 1, entries 7, 8, 15, and 16).
A small amount of hexamethylphosphoramide as a co-
solvent and heating to 60 °C was necessary for these reac-
tions. However, similar reactions employing 3c were
unsuccessful.
(Diphenylphosphoryl)methyl Phenylethynyl Chalcogenides
2a–c; General Procedure
A soln of BuLi (11 mmol) was added to a soln of phenylacetylene
(1.12 g, 11 mmol) in THF (15 mL), under an argon atmosphere, at
0 °C. The mixture was stirred at 0 °C for 20 min , then S, Se, or Te
In summary, we described a highly convenient method for
the preparation of alkynyl vinyl chalcogenides through
Synthesis 2009, No. 3, 469–473 © Thieme Stuttgart · New York

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Stereoselective Synthesis of Alkynyl Vinyl Chalcogenides
471
(11 mmol) was added and the mixture was further stirred at r.t. until
consumption of the chalcogen. Then, a soln of (diphenylphosphor-
yl) methyl p-toluenesulfonate (1, 3.86 g, 10 mmol) in THF (20 mL)
was added at 0 °C and the mixture was stirred at r.t. for 2 h (3.5 h
for the sulfur derivative). H2O (50 mL) was added, the mixture was
extracted with EtOAc (3 × 50 mL), and the combined organic layers
were washed with brine (50 mL). The organic layer was dried
(MgSO4) and the solvent was removed under reduced pressure. The
residue was purified by column chromatography (hexanes–EtOAc,
7:3).
Phenylethynyl Styryl Sulfide (3a)
Mp 36–39 °C; ratio E/Z 11:1.
IR (KBr): 1603, 2166 cm–1.
1H NMR (200 MHz, CDCl3): d = 6.57 (d, J = 15.0 Hz, 1 H), 6.86 (d,
J = 15.0 Hz, 1 H), 7.18–7.36 (m, 8 H), 7.47–7.53 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 74.5, 98.7, 118.6, 122.7, 126.0,
127.6, 128.4, 128.7, 129.6, 131.6, 135.9.
MS (EI): m/z (%) = 236 (58, M+).
Anal. Calcd for C16H12S: C, 81.31; H, 5.12. Found: C, 81.17; H,
5.03.
(Diphenylphosphoryl)methyl Phenylethynyl Sulfide (2a)
Mp 105–107 °C.
IR (KBr): 1183 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.65 (d, JP-H = 8.0 Hz, 2 H), 7.24–
7.26 (m, 5 H), 7.49–7.56 (m, 6 H), 7.78–7.88 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 34.1 (d, JP-C = 66.7 Hz), 78.0 (d,
JP-C = 6.1 Hz), 93.2, 122.5, 128.0, 128.3, 128.5 (d, JP-C = 12.2 Hz),
131.1 (d, JP-C = 9.9 Hz), 131.5, 132.2 (d, JP-C = 3.0 Hz).
4-Methylstyryl Phenylethynyl Sulfide (3c)
Mp 64–66 °C; ratio E/Z 11:1.
IR (KBr): 1595, 2172 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.30 (s, 3 H), 6.47 (d, J = 15.0 Hz,
1 H), 6.81 (d, J = 15.0 Hz, 1 H), 7.09 (d, J = 8.0 Hz, 2 H), 7.20 (d,
J = 8.0 Hz, 2 H), 7.29–7.31 (m, 3 H), 7.46–7.49 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 21.1, 74.9, 98.3, 117.4, 122.8,
125.9, 128.3, 128.5, 129.3, 129.8, 131.6, 133.2, 137.5.
MS (EI): m/z (%) = 348 (53, M+).
Anal. Calcd for C21H17OPS: C, 72.40; H, 4.92. Found: C, 71.57; H,
4.97.
MS (EI): m/z (%) = 250 (68, M+), 249 (29), 235 (36), 234 (73), 205
(25), 202 (38), 121 (100), 115 (35), 91 (21), 89 (41), 65 (26), 63
(24).
(Diphenylphosphoryl)methyl Phenylethynyl Selenide (2b)
Anal. Calcd for C17H14S: C, 81.56; H, 5.64. Found: C, 81.13; H,
5.41.
Mp 131–132 °C.
IR (KBr): 1188 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.66 (d, JP-H = 6.9 Hz, 2 H), 7.26–
7.28 (m, 5 H), 7.44–7.55 (m, 6 H), 7.77–7.88 (m, 4 H).
4-Chlorostyryl Phenylethynyl Sulfide (3d)
Mp 64–67 °C; ratio E/Z 9:1.
13C NMR (100 MHz, CDCl3): d = 25.8 (d, JP-C = 67.0 Hz), 69.8 (d,
JP-C = 6.3 Hz), 99.6, 122.8, 128.0, 128.3, 128.5 (d, JP-C = 12.0 Hz),
131.0 (d, JP-C = 9.9 Hz), 131.3 (d, JP-C = 103.1 Hz), 131.5, 132.1 (d,
JP-C = 2.8 Hz).
IR (KBr): 1603, 2161 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.53 (d, J = 15.0 Hz, 1 H), 6.78 (d,
J = 15.0 Hz, 1 H), 7.22 (d, J = 8.7 Hz, 2 H), 7.26 (d, J = 8.7 Hz, 2
H), 7.31–7.34 (m, 3 H), 7.48–7.50 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 74.2, 99.0, 119.6, 122.6, 127.2,
128.1, 128.4, 128.8, 128.8, 131.7, 133.2, 134.5.
MS (EI): m/z (%) = 270 (37, M+), 235 (30), 234 (82), 225 (17), 202
(36), 121 (100), 117 (19), 102 (20), 101 (29), 89 (37), 75 (28), 63
(17), 51 (20).
MS (EI): m/z (%) = 396 (20, M+).
Anal. Calcd for C21H17OPSe: C, 63.81; H, 4.33. Found: C, 63.53; H,
4.13.
(Diphenylphosphoryl)methyl Phenylethynyl Telluride (2c)
Mp 139–142 °C.
Anal. Calcd for C16H11ClS: C, 70.97; H, 4.09. Found: C, 70.71; H,
3.95.
IR (KBr): 1178 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.76 (d, JP-H = 7.3 Hz, 2 H), 7.25–
7.33 (m, 5 H), 7.42–7.52 (m, 6 H), 7.70–7.86 (m, 4 H).
Pent-1-enyl Phenylethynyl Sulfide (3f)
13C NMR (100 MHz, CDCl3): d = 6.87 (d, JP-C = 67.5 Hz), 45.8 (d,
JP-C = 6.1 Hz), 112.0, 123.0, 128.1, 128.5, 128.6 (d, JP-C = 11.5 Hz),
130.9 (d, JP-C = 9.9 Hz), 131.8, 132.0 (d, JP-C = 102.7 Hz), 132.1 (d,
JP-C = 3.1 Hz).
Oil; ratio E/Z 2:1.
IR (KBr): 1593, 2165 cm–1.
1H NMR (400 MHz, CDCl3): d (E form) = 0.92 (t, J = 7.3 Hz, 3 H),
1.44 (sext, J = 7.3 Hz, 2 H), 2.13 (dq, J = 7.3, 1.2 Hz, 2 H), 5.87 (dt,
J = 14.7, 1.2 Hz, 1 H), 5.99 (dt, J = 14.7, 6.8 Hz, 1 H), 7.28–7.31
(m, 3 H), 7.40–7.47 (m, 2 H); d (Z form) = 0.94 (t, J = 7.3 Hz, 3 H),
1.45 (sext, J = 7.3 Hz, 2 H), 2.12 (dq, J = 7.3, 1.4 Hz, 2 H), 5.75 (dt,
J = 9.0, 7.3 Hz, 1 H), 6.12 (dt, J = 9.0, 1.4 Hz, 1 H), 7.28–7.31 (m,
3 H), 7.40–7.47 (m, 2 H),
13C NMR (100 MHz, CDCl3): d (E + Z form) = 13.5, 13.6, 21.9,
22.1, 30.6, 34.7, 76.1, 77.7, 92.9, 96.7, 117.3, 121.8, 123.0, 123.1,
128.2, 128.2, 128.3, 128.3, 131.4, 131.5, 132.7, 132.9.
MS (EI): m/z (%) = 354 (17).
Anal. Calcd for C21H17OPTe: C, 56.82; H, 3.86. Found: C, 57.11; H,
3.67.
Alkynyl Phenylethynyl Chalcogenides 3a–h, 4a–h, and 5a–e;
General Procedure
To a soln of (diphenylphosphoryl)methyl phenylethynyl chalco-
genide 2 (1 mmol) in THF (10 mL) was added 95% NaH (51 mg, 2
mmol) at 0 °C. After 20 min, the appropriate carbonyl compound
(1.5 mmol) was added at 0 °C and the reaction was stirred at r.t. [ke-
tones: at 60 °C and with HMPA (1 mL)] for the time indicated in
Table 1. Sat. aq NH4Cl was added and the mixture was extracted
with EtOAc (3 × 20 mL). The organic layer was dried (MgSO4), fil-
tered, and concentrated under reduced pressure. The residue was
purified by column chromatography (hexanes).
MS (EI): m/z (%) = 202 (54, M+).
Anal. Calcd for C13H14S: C, 77.18; H, 6.97. Found: C, 77.98; H,
6.73.
2,2-Diphenylvinyl Phenylethynyl Sulfide (3h)
Mp 51–52 °C.
IR (KBr): 1591, 2171 cm–1.
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C. C. Silveira et al.
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1H NMR (200 MHz, CDCl3): d = 6.77 (s, 1 H), 7.19–7.45 (m, 15 H).
13C NMR (50 MHz, CDCl3): d = 77.8, 93.8, 121.9, 123.8, 127.0,
127.6, 128.1, 128.3, 128.3, 128.3, 128.5, 129.5, 131.5, 137.9, 140.4,
141.9.
Anal. Calcd for C16H11ClSe: C, 60.49; H, 3.49. Found: C, 60.50; H,
3.48.
2,2-Diphenylvinyl Phenylethynyl Selenide (4h)
Mp 80–82 °C.
IR (KBr): 1591, 2156 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.11 (s, 1 H), 7.22–7.34 (m, 6 H),
7.37–7.48 (m, 9 H).
MS (EI): m/z (%) = 312 (57, M+).
Anal. Calcd for C22H16S: C, 84.57; H, 5.16. Found: C, 84.43, H,
5.05.
Phenylethynyl Styryl Selenide (4a)
Mp 55–56 °C; ratio E/Z 9:1.
13C NMR (50 MHz, CDCl3): d = 70.6, 99.6, 119.6, 123.1, 127.0,
127.6, 128.3, 128.8, 128.9, 131.6, 139.1, 140.3, 143.9.
IR (KBr): 1600, 2162 cm–1.
MS (EI): m/z (%) = 360 (2, M+).
1H NMR (400 MHz, CDCl3): d = 6.89 (d, J = 15.4 Hz, 1 H), 7.01 (d,
J = 15.4 Hz, 1 H), 7.21–7.35 (m, 8 H), 7.48–7.50 (m, 2 H).
Anal. Calcd for C22H16Se: C, 73.54; H, 4.49. Found: C, 73.32; H,
4.40.
13C NMR (100 MHz, CDCl3): d = 67.8, 103.5, 115.1, 123.0, 126.1,
4-Methoxystyryl Phenylethynyl Telluride (5b)
Mp 119–121 °C; ratio E/Z 12:1.
IR (KBr): 1602, 2151 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.81 (s, 3 H), 6.86 (d, J = 8.8 Hz,
2 H), 7.09 (d, J = 16.7 Hz, 1 H), 7.21 (d, J = 16.7 Hz, 1 H), 7.30–
7.35 (m, 5 H), 7.45–7.50 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 46.0, 55.2, 94.8, 113.7, 113.9,
123.3, 127.5, 128.2, 128.5, 130.7, 131.8, 142.2, 159.5.
127.7, 128.3, 128.5, 128.6, 131.6, 133.6, 136.5.
MS (EI): m/z (%) = 284 (15, M+), 283 (7), 282 (12), 204 (100), 203
(84), 202 (69), 169 (26), 102 (39), 101 (45), 89 (33), 77 (49), 51
(34).
Anal. Calcd for C16H12Se: C, 67.85; H, 4.27. Found: C, 67.61; H,
4.27.
4-Methoxystyryl Phenylethynyl Selenide (4b)
Mp 107–108 °C; ratio E/Z 16:1.
IR (KBr): 1600, 2162 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.78 (s, 3 H), 6.74 (d, J = 15.3 Hz,
1 H), 6.84 (d, J = 8.7 Hz, 2 H), 6.96 (d, J = 15.3 Hz, 1 H), 7.26 (d,
J = 8.7 Hz, 2 H), 7.30–7.32 (m, 3 H), 7.47–7.49 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 55.2, 68.3, 102.9, 112.0, 114.1,
123.1, 127.4, 128.3, 128.4, 129.4, 131.6, 133.7, 159.4.
MS (EI): m/z (%) = 314 (17, M+).
MS (EI): m/z (%) = 364 (8, M+), 267 (18), 266 (100).
Anal. Calcd for C17H14OTe: C, 56.42; H, 3.90. Found: C, 56.09; H,
3.76.
Acknowledgment
We are indebted to the CAPES, MCT/CNPq, and FAPERGS for fi-
nancial support.
Anal. Calcd for C17H14OSe: C, 65.18; H, 4.50. Found: C, 65.16; H,
4.48.
References
(1) (a) Tang, Y.; Ye, S.; Sun, X. L. Synlett 2005, 2720.
(b) Petragnani, N.; Stefani, H. A. Tetrahedron 2005, 61,
1613. (c) Ranganathan, S.; Muraleedharan, K. M.; Vaish, N.
K.; Jayaraman, N. Tetrahedron 2004, 60, 5273.
(d) Aggarwal, V. K.; Winn, C. L. Acc. Chem. Res. 2004, 37,
611. (e) Comasseto, J. V.; Barrientos-Astigarraga, R. E.
Aldrichimica Acta 2000, 33, 66. (f) Wessjohann, L. A.;
Sinks, U. J. Prakt. Chem. 1998, 340, 189. (g) Radchenko,
S. I.; Petrov, A. A. Russ. Chem. Rev. (Engl. Transl.) 1989,
58, 948. (h) Engman, L. Acc. Chem. Res. 1985, 18, 274.
(2) (a) Petragnani, N.; Stefani, H. A. Tellurium in Organic
Synthesis, In Best Synthetic Methods; Academic Press:
London, 2007, 2nd ed.. (b) Stang, P. J.; Zhdankin, V. V. In
Comprehensive Organic Functional Group
4-Methylstyryl Phenylethynyl Selenide (4c)
Mp 62–63 °C; ratio E/Z 12:1.
IR (KBr): 1595, 2152 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.31 (s, 3 H), 6.83 (d, J = 15.3 Hz,
1 H), 6.98 (d, J = 15.3 Hz, 1 H), 7.11 (d, J = 8.1 Hz, 2 H), 7.22 (d,
J = 8.1 Hz, 2 H), 7.30–7.32 (m, 3 H), 7.47–7.49 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 21.2, 68.1, 103.2, 113.7, 123.1,
126.1, 128.3, 128.5, 129.3, 129.3, 131.6, 133.7, 137.7.
MS (EI): m/z (%) = 298 (14, M+).
Anal. Calcd for C17H14Se: C, 68.69; H, 4.75. Found: C, 68.62; H,
4.70.
Transformations, Vol. 2; Katritzky, A. R.; Meth-Cohn, O.;
Rees, C. W., Eds.; Elsevier: Oxford, 1995, Chap 21.
(c) Whitham, G. H. Organosulfur Chemistry, In Oxford
Chemistry Primers; Davies, S. G., Ed.; Oxford University
Press: Oxford, 1995. (d) Petragnani, N. Tellurium in
Comprehensive Organometallic Chemistry, Vol. 11;
McKillop, A., Ed.; Pergamon: Oxford, 1995. (e) The
Chemistry of Organic Selenium and Tellurium Compounds,
Vol. 1; Patai, S.; Rappoport, Z., Eds.; Wiley: Chichester,
1986. (f) Irgolic, K. Y. In Houben-Weyl, 4th ed., Vol. E12b;
Klamann, D., Ed.; Georg Thieme Verlag: Stuttgart, 1990.
4-Chlorostyryl Phenylethynyl Selenide (4d)
Mp 94–96 °C; ratio E/Z 9:1.
IR (KBr): 1600, 2162 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.88 (d, J = 15.3 Hz, 1 H), 6.95 (d,
J = 15.3 Hz, 1 H), 7.24 (d, J = 8.3 Hz, 2 H), 7.28 (d, J = 8.3 Hz, 2
H), 7.32–7.34 (m, 3 H), 7.48–7.51 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 67.4, 103.9, 116.0, 122.9, 127.3,
128.4, 128.7, 128.8, 131.7, 132.0, 133.4, 135.0.
MS (EI): m/z (%) = 318 (9, M+), 238 (66), 203 (53), 202 (100), 169
(27), 102 (52), 101 (75), 89 (42), 75 (44), 51 (32).
Synthesis 2009, No. 3, 469–473 © Thieme Stuttgart · New York

PAPER
(3) (a) Perez-Balado, C.; Markó, I. E. Tetrahedron 2006, 62,
Stereoselective Synthesis of Alkynyl Vinyl Chalcogenides
(10) (a) Bassora, B. K.; Da Costa, C. E.; Gariani, R. A.;
473
2331. (b) Bieber, L. W.; da Silva, M. F.; Menezes, P. H.
Tetrahedron Lett. 2004, 45, 2735. (c) Braga, A. L.; Martins,
T. L.; Silveira, C. C.; Rodrigues, O. E. D. Tetrahedron 2001,
57, 3297. (d) Su, H.; Yu, W.; Jin, Z. Tetrahedron Lett. 2001,
42, 3771. (e) Braga, A. L.; Silveira, C. C.; Reckziegel, A.;
Menezes, P. H. Tetrahedron Lett. 1993, 34, 8041. (f)Braga,
A. L.; Reckziegel, A.; Menezes, P. H.; Stefani, H. A.
Tetrahedron Lett. 1993, 34, 393. (g) Tingoli, M.; Tiecco,
M.; Testaferri, L.; Temperini, A. Tetrahedron 1995, 51,
4691.
Comasseto, J. V.; Dos Santos, A. A. Tetrahedron Lett. 2007,
48, 1485; and references therein. (b) Seebach, D.; Beck, A.
K. Chem. Ber. 1975, 108, 314. (c) Kauffman, T. Angew.
Chem., Int. Ed. Engl. 1982, 21, 4110. (d) Barros, S. M.;
Comasseto, J. V.; Berriel, J. Tetrahedron Lett. 1989, 30,
7353. (e) Tucci, F. C.; Chieffi, A.; Comasseto, J. V.; Marino,
J. P. J. Org. Chem. 1996, 61, 4975. (f)Terao, J.;Kambe, N.;
Sonoda, N. Tetrahedron Lett. 1996, 37, 4741. (g)Huang, Y.
Z.; Mo, X. S. Synlett 1998, 93. (h) Mo, X. S.; Huang, Y. Z.
Tetrahedron Lett. 1995, 36, 3539. (i) Jang, W. B.; Oh, D.
Y.; Lee, C. W. Tetrahedron Lett. 2000, 41, 5103.
(11) Busi, E.; Capozzi, G.; Menichetti, S.; Nativi, C. Synthesis
1992, 643.
(4) (a) Lüdtke, D. S.; Panatieri, R. B.; Braga, A. L.; Zeni, G.
Chem. Rev. 2006, 106, 1032. (b) Araujo, M. A.; Raminelli,
C.; Comasseto, J. V. J. Braz. Chem. Soc. 2004, 15, 358.
(c) Silveira, C. C.; Perin, G.; Jacob, R. G.; Braga, A. L.
Phosphorus, Sulfur Silicon Relat. Elem. 2001, 172, 309.
(d) Comasseto, J. V.; Ling, L. W.; Petragnani, N.; Stefani, H.
A. Synthesis 1997, 373.
(5) (a) Zhdankin, V. V. In Comprehensive Organic Functional
Group Transformations II, Vol. 2; Katritzky, A. R.; Taylor,
R. J. K., Eds.; Pergamon: New York, 2005, Chap. 21.
(b) Braga, A. L.; Reckziegel, A.; Silveira, C. C.; Comasseto,
J. V. Synth. Commun. 1994, 24, 1165. (c) 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.
(6) (a) Gerard, J.; Hevesi, L. Tetrahedron 2001, 57, 9109.
(b) Tingoli, M.; Tiecco, M.; Testaferri, L.; Temperini, A.;
Pelizzi, G.; Bacci, A. Tetrahedron 1995, 51, 4691.
(c) Tingoli, M.; Tiecco, M.; Testaferri, L.; Chianelli, D.
Gazz. Chim. Ital. 1991, 121, 59. (d) Okamura, H.; Miura,
M.; Kosugi, K.; Takei, H. Tetrahedron Lett. 1980, 21, 87.
(e) Silveira, C. C.; Santos, P. C. S.; Braga, A. L. Tetrahedron
Lett. 2002, 43, 7517.
(12) Brandsma, L.; Arens, J. F. Recl. Trav. Chim. Pays-Bas 1961,
80, 237.
(13) Verboom, W.; Meijer, J.; Brandsma, L. Synthesis 1978, 577.
(14) Verboom, W.; Sukhai, R. S.; Meijer, J. Synthesis 1979, 47.
(15) Ehrhardt, H.; Ertel, H.; Mildenberger, H.; Sachse, B.; Hartz,
P. DE 2821639, 1979; Chem. Abstr. 1980, 92, 180132.
(16) (a) Silveira, C. C.; Cella, R.; Braga, A. L.; Jacob, R. G.;
Lenardão, E. J.; Perin, G. Tetrahedron 2005, 61, 7712.
(b) Silveira, C. C.; Guadagnin, R. C.; Braga, A. L.
Tetrahedron Lett. 2003, 44, 5703. (c) Silveira, C. C.;
Santos, P. C. S.; Braga, A. L. Tetrahedron Lett. 2002, 43,
7517. (d) Silveira, C. C.; Perin, G.; Braga, A. L.; Dabdoub,
M. J.; Jacob, R. G. Tetrahedron 2001, 57, 5953.
(e) Silveira, C. C.; Nunes, M. R. S.; Wendling, E.; Braga, A.
L. J. Organomet. Chem. 2001, 623, 131. (f) Silveira, C. C.;
Boeck, P.; Begnini, M. L.; Braga, A. L. Phosphorus, Sulfur
Silicon Relat. Elem. 2001, 172, 427. (g) Silveira, C. C.;
Boeck, P.; Braga, A. L. Tetrahedron Lett. 2000, 41, 1867.
(h) Silveira, C. C.; Perin, G.; Boeck, P.; Braga, A. L.;
Petragnani, N. J. Organomet. Chem. 1999, 584, 44.
(i) Silveira, C. C.; Perin, G.; Braga, A. L.; Dabdoub, M. J.;
Jacob, R. G. Tetrahedron 1999, 55, 7421. (j)Silveira, C. C.;
Begnini, M. L.; Boeck, P.; Braga, A. L. Synthesis 1997, 221.
(k) Silveira, C. C.; Perin, G.; Braga, A. L.; Petragnani, N.
Synlett 1995, 58.
(7) (a) Mehta, V. P.; Sharma, A.; Van der Eycken, E. Org. Lett.
2008, 10, 1147. (b) Hevesi, L.; Hermans, B.; Allard, C.
Tetrahedron Lett. 1994, 35, 6729.
(8) Zeni, G.; Braga, A. L.; Stefani, H. A. Acc. Chem. Res. 2003,
36, 731.
(9) (a) Raminelli, C.; Gargalaka, J. Jr.; Silveira, C. C.;
Comasseto, J. V. Tetrahedron 2007, 63, 8801.
(17) Silveira, C. C.; Rinaldi, F.; Guadagnin, R. C. Eur. J. Org.
(b) Raminelli, C.; Gargalaka, J. Jr.; Silveira, C. C.;
Comasseto, J. V. Tetrahedron Lett. 2004, 45, 4927.
(c) Silveira, C. C.; Braga, A. L.; Vieira, A. S.; Zeni, G.
J. Org. Chem. 2003, 68, 662.
Chem. 2007, 4935.
(18) Clayden, J.; Warren, S. Angew. Chem., Int. Ed. Engl. 1996,
35, 241.
Synthesis 2009, No. 3, 469–473 © Thieme Stuttgart · New York