Copper-catalyzed cross-coupling of thiols with 1-iodo-2-chalcogenoalkenes

Article abstract of DOI:10.1002/ejoc.200800495

We describe herein a new method for the synthesis of densely substituted alkenes containing chalcogenide atoms by a cross-coupling reaction between 1-iodo-2-chalcogenoalkenes and thiols using copper(I) as catalyst in a ligand-free system. The desired cross-coupling products were obtained in good yields and with satisfactory selectivity. The developed protocol tolerates a wide range of functional groups; the reactions of alkyl-, benzyl-, and arylthiols with neutral, electron-deficient, and electron-rich substituents on the aromatic ring were explored in the absence of any supplementary additives. In addition, the reaction proceeded cleanly under mild reaction conditions and was sensitive to the nature of the catalyst, base, and solvent. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejoc.200800495

FULL PAPER
DOI: 10.1002/ejoc.200800495
Copper-Catalyzed Cross-Coupling of Thiols with 1-Iodo-2-chalcogenoalkenes
Flávia Manarin,[a] Juliano A. Roehrs,[a] Ethel A. Wilhelm,[a] and Gilson Zeni*[a]
Keywords: Copper / Cross-coupling / Organoselenium compounds / Thiols
We describe herein a new method for the synthesis of
densely substituted alkenes containing chalcogenide atoms
neutral, electron-deficient, and electron-rich substituents on
the aromatic ring were explored in the absence of any sup-
plementary additives. In addition, the reaction proceeded
by
a cross-coupling reaction between 1-iodo-2-chalcog-
enoalkenes and thiols using copper(I) as catalyst in a ligand- cleanly under mild reaction conditions and was sensitive to
free system. The desired cross-coupling products were ob- the nature of the catalyst, base, and solvent.
tained in good yields and with satisfactory selectivity. The
developed protocol tolerates a wide range of functional
groups; the reactions of alkyl-, benzyl-, and arylthiols with
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
Over the past few years, great progress has been made
in carbon–heteroatom bond formation through the cross-
coupling reaction of nucleophilic species with halides using
a copper-catalyzed system.[6] These improvements are cer-
tainly a consequence of the studies into the effects of several
ligands, such as aliphatic diamines, 1,10-phenanthroline,
amino acids and their derivatives, and others, on these reac-
tions. These important findings have allowed the use of
common organic solvents (dichloromethane, chloroform,
toluene, benzene, DMF, and DMSO) and weaker bases
(K2CO3, Cs2CO3, and K3PO4), and they also allow the use
of not only aryl iodide, but also aryl bromides and chlo-
rides. After that, these reactions became more attractive as
nowadays they can be carried out at lower temperatures,
under milder conditions, and by using a catalytic amount
of the copper salts. In contrast, there are no reports on the
use of halogenated vinylchalcogen compounds as electro-
philic substrates for the formation of carbon–sulfur bonds
using palladium or copper cross-coupling reactions.[7] Be-
cause of the advantages of using copper catalysts, less ex-
pensive and toxic than palladium salts, we have investigated
a new methodology for building carbon–sulfur bonds[8] by
using a copper-catalyzed coupling reaction between 1-iodo-
2-chalcogenoalkenes and thiols without any ligands or co-
catalysts (Scheme 1).
Introduction
The stereoselective synthesis of densely functionalized al-
kenes is an important subject in organic chemistry owing
to the fact that many biologically active compounds have
these units in their structures. In particular, in recent years,
there has been remarkable interest in the synthesis of vinylic
chalcogenides and their synthetic application in the devel-
opment of methodologies for the synthesis of substituted
alkenes.[1] There are several reasons for this, including a
wide synthetic potential and the fact that the chalcogenide
atom exercises a stabilizing effect on neighboring positive
as well as negative charges. This makes the double bond in
vinylic chalcogenides responsive towards both nucleophilic
and electrophilic attack, an extremely useful feature in or-
ganic synthesis.[2]
The scope and application of organosulfur chemistry has
increased tremendously because sulfur-containing groups
serve as an important auxiliary function in synthetic se-
quences. Most of the synthetic transformations that use or-
ganosulfur compounds have involved the use of vinylic sul-
fides.[3] Many procedures for the preparation of vinyl sul-
fides have been developed.[4] In the course of our study on
the preparation of vinyl sulfides and their application in
organic synthesis, we have reported the introduction of two
thiol groups onto the double bond.[5]
[a] Laboratório de Síntese, Reatividade, Avaliação Farmacológica
e Toxicológica de Organocalcogênios, CCNE, Universidade
Federal de Santa Maria,
Santa Maria, Rio Grande do Sul 97105-900, Brazil
Fax: +55-55-3220-8998
E-mail: gzeni@quimica.ufsm.br
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
Scheme 1. General scheme for the copper-catalyzed cross-coupling
reaction.
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Cross-Coupling of Thiols with 1-Iodo-2-chalcogenoalkenes
Table 1. Optimization of the conditions for the cross-coupling reac-
tion.
Results and Discussion
The starting 1-iodo-2-chalcogenoalkene was readily
available by stereoselective addition of benzeneselenenyl io-
dide to substituted alkynes 1 in benzene at room tempera-
ture, affording the desired products in good yields after pu-
rification (Scheme 2). Regarding the stereochemistry of
these tetrasubstituted alkenes, the formation of trans ad-
ducts was observed.[9] However, compounds 2a–c were ob-
tained as a mixture of regioisomers (85:15)) with the re-
gioisomer shown in Scheme 2 predominating.
Entry Copper salt[a]
Base
Solvent
Yield of 3c[b]
1
2
3
4
5
6
Cu(OAc)2
CuCl
CuCN
CuCl2
CuBr2
CuI
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
KOH
Na2CO3
Cs2CO3
K2CO3
Et3N
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
THF
73%
72%
64%
66%
65%
79%
60%
72%
74%
44%
80%
40%
48%
71%
25%
7
8
CuI
CuI
9
CuI
CuI
CuI
CuI
CuI
CuI
CuI
10
11
12
13
14
15
pyrrolidine
Et3N
Et3N
toluene
DMF
Scheme 2.
Et3N
[a] 10 mol-%. [b] The reactions were carried out for 12 h.
Our initial studies on the cross-coupling reaction focused
on the optimization of the reaction conditions. In this way,
the reaction was performed with [(E)-1-iodo-2-(phenylsel-
anyl)oct-1-enyl](methyl)sulfane (2b) and benzenethiol.
Thus, a mixture of 2b (0.5 mmol), thiol (0.6 mmol), and
K3PO4 (1 mmol) was treated with different copper salts in
dioxane (2.5 mL) as solvent (Table 1). According to Table 1,
the cross-coupling reaction of 2b with benzenethiol was best
catalyzed by CuI (Table 1, Entry 11). By using this catalyst
(10 mol-%) the desired product 3c was obtained in a good
yield of 80%. Other copper salts such as CuCl, CuCN,
CuCl2, CuBr2, and Cu(OAc)2 were less effective (Table 1,
Entries 1–5). The nature of the base was also critical for the
success of the cross-coupling reaction. When different bases
such as K2CO3, K3PO4, KOH, Na2CO3, Cs2CO3, and pyr-
rolidine were used instead of Et3N, moderate yields of the
desired product 3c were obtained (Table 1, Entries 7–10 and
12).
Scheme 3.
protocol, we explored the generality of our method by ap-
plying these conditions to different thiols and other vinyl
iodides. The results are summarized in Table 2.
We then explored the coupling of different vinyl iodides;
both selenide and sulfide gave the desired products in good
yields. Regarding the thiol, our experiments showed that
the reaction with high-boiling alkanethiols gave the product
in moderate yields (Table 2, Entry 18). Conversely, low-boil-
ing alkanethiols such as propanethiol did not give the de-
sired product (Table 2, Entry 9).
Regarding the influence of solvent on this coupling reac-
tion, optimal results were obtained by using dioxane
(Table 1, Entry 11). By using THF or DMF, the desired
product 3c was obtained in unacceptable yields (Table 1;
Entries 13 and 15, respectively).
In view of the fact that heterocycles occur in many com-
pounds of biological interest, we attempted to broaden the
We also investigated the influence of the halide atom in scope of our methodology by performing the reaction with
the vinylic substrate and observed that the vinyl iodide and heterocyclic thiols. It was found that the reaction worked
bromide gave the products in good-to-moderate yields, well, affording the desired coupling products in satisfactory
respectively. However, when the vinyl chloride was used, the yields (Table 2, Entries 6–8 and 13–15). Note that this
product was not obtained, and the starting material was method showed efficient selectivity with 2-mercaptoethanol
quantitatively recovered (Scheme 3).
in which both a hydroxy and a thiol group are present. The
Careful analysis of the optimization reactions revealed thiol group reacted preferentially with the vinyl iodide
that the optimum conditions for the coupling reaction were (Table 2, Entry 10) and not with the hydroxy group;[10] it is
the use of CuI (10 mol-%), [(E)-1-iodo-2-(phenylselanyl)oct- well known that iodides can react with alcohols under cop-
1-enyl](methyl)sulfane (2b) (0.5 mmol), benzenethiol per catalysis. Moreover, we also investigated the differences
(0.6 mmol), and Et3N (1 mL) in dioxane (2.5 mL) at reflux in the reactivity of an amine and a thiol group (Table 2,
temperature for 12 h. To demonstrate the efficiency of this Entries 8 and 15); no side-reactions with the amine group
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F. Manarin, J. A. Roehrs, E. A. Wilhelm, G. Zeni
FULL PAPER
Table 2. Cross-coupling products obtained by using vinyl iodides 2a–c and thiols.
[a] Yields of 3a–q are given for isolated products. [b] The products were obtained as regioisomers in a ratio of 85:15.
4462 Eur. J. Org. Chem. 2008, 4460–4465
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Cross-Coupling of Thiols with 1-Iodo-2-chalcogenoalkenes
General Procedure for the Cross-Coupling Reaction: The thiol
(0.6 mmol) was added to a Schlenk tube maintained under argon
containing an appropriate vinyl iodide (0.50 mmol) in dioxane
(3 mL). After this, Et3N was added dropwise (1 mmol), followed
by CuI (10 mol-%), and the reaction mixture was stirred at reflux
temperature for 12 h. After this, the mixture was diluted with ethyl
acetate (20 mL) and washed with brine (3 ϫ 20 mL). The organic
phase was separated, dried with MgSO4, and concentrated under
vacuum. The residue was purified by flash chromatography on sil-
ica gel using hexane as the eluent.
were observed. To the best of our knowledge, iodides ef-
ficiently react with amines to afford carbon–nitrogen prod-
ucts in the presence of copper catalysts.[11] It is also impor-
tant to point out that the configuration of the double bond
in the product, determined by X-ray diffraction analysis,
was the same as in the vinyl iodide, which demonstrates that
this reaction is highly regio- and stereospecific.
Conclusions
Methyl[(E)-2-phenyl-2-(phenylselanyl)-1-(phenylthio)vinyl]sulfane
1
(3a): Yield 0.165 g (80%). H NMR (CDCl3, 200 MHz): δ = 7.30–
We have explored the thiol cross-coupling reaction of al-
kenes containing a chalcogenide with CuI in the absence of
any supplementary additives. This method tolerated a wide
range of functional groups in the thiol or vinyl substrates.
The advantages of CuI in a ligand-free system include its
lower cost, which is important when considering the scale-
up of a reaction. In addition, the reaction proceeded cleanly
under mild reaction conditions and was sensitive to the na-
ture of the catalyst, base, and solvent. The pharmacological
activities of these compounds are under study in our labo-
ratory. We expect that these findings would be useful in
choosing a method for the synthesis of functionalized al-
kynes. This reaction, more generally associated with the
nickel-catalyzed cross-coupling of selenides,[12] is an inter-
esting alternative route to the preparation of more function-
alized alkynes.
7.22 (m, 2 H), 7.0–6.93 (m, 9 H), 2.37 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 146.9, 138.7, 135.9, 129.6, 129.1, 129.0,
128.7, 128.3, 127.8, 127.3, 127.1, 127.0, 126.0, 125.2, 17.2 ppm. MS
(%): m/z (%) = 414 (25), 258 (22), 210 (100), 178 (25), 89 (28).
HRMS: calcd. for C21H18S2Se 414.0015; found 414.0011.
(2-Chlorophenyl)[(E)-1-(methylthio)-2-phenyl-2-(phenylselanyl)vinyl-
]sulfane (3b): Yield 0.160 g (72%). 1H NMR (CDCl3, 200 MHz),:
δ = 7.31–7.25 (m, 5 H), 7.10–6.95 (m, 9 H), 2.36 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 148.8, 138.4, 136.0, 135.2, 131.9,
129.4, 129.3, 129.1, 128.9, 128.3, 127.9, 127.4, 127.2, 126.9, 126.8,
123.6, 17.5 ppm. MS (%): m/z (%) = 448 (10), 258 (40), 244 (100),
178 (29), 133 (50), 89 (60). HRMS: calcd. for C21H17ClS2Se
447.9625; found 447.9630.
Methyl[(E)-2-(phenylselanyl)-1-(phenylthio)oct-1-enyl]sulfane (3c):
1
Yield 0.168 g (80%). H NMR (CDCl3, 400 MHz): δ = 2.29 (s, 3
H), 1.29 (quint, J = 7.0 Hz, 2 H), 1.10 (quint, J = 7.0 Hz, 2 H),
1.0–0.92 (m, 4 H), 0.76 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 151.8, 136.5, 129.4, 129.0, 128.8, 128.6,
128.0, 127.7, 125.9, 121.7, 35.7, 31.2, 29.7, 28.6, 22.3, 17.3,
13.9 ppm. MS (%): m/z (%) = 422 (100), 193 (40), 147 (73), 107
(60), 79 (50). HRMS: calcd. for C21H26S2Se 422.0641; found
422.0637.
Experimental Section
General: Proton nuclear magnetic resonance spectra (1H NMR)
were obtained at 200 MHz on a Bruker DPX-200 NMR spectrome-
ter or at 400 MHz on a Bruker DPX-400 NMR spectrometer. Spec-
tra were recorded in CDCl3 solutions. Chemical shifts are reported
in ppm, referenced to the solvent peak of CDCl3 or tetramethylsil-
ane (TMS) as the external reference. Data are reported as follows:
chemical shift (δ), multiplicity, coupling constant (J) in Hertz and
integrated intensity. Carbon-13 nuclear magnetic resonance spectra
(13C NMR) were obtained either at 50 MHz on a Bruker DPX-200
NMR spectrometer or at 100 MHz on a Bruker DPX-400 NMR
spectrometer. Spectra were recorded in CDCl3 solutions. Chemical
shifts are reported in ppm, referenced to the solvent peak of
CDCl3. Abbreviations to denote the multiplicity of a particular sig-
nal are s (singlet), d (doublet), t (triplet), q (quartet), quint (quin-
tet), dt (double triplet), td (triple doublet) and m (multiplet). Col-
umn chromatography was performed using Merck silica gel (230-
400 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. Most reactions were monitored by
TLC for disappearance of the starting material. The following sol-
vents were dried and purified by distillation from the reagents indi-
cated: tetrahydrofuran from sodium with a benzophenone ketyl in-
dicator. All other solvents were ACS or HPLC grade unless other-
wise noted. Air- and moisture-sensitive reactions were conducted
in flame- or oven-dried glassware equipped with tightly fitted rub-
ber septa and under an atmosphere of dry nitrogen or argon. Rea-
gents and solvents were handled using standard syringe techniques.
(2-Chlorophenyl)[(E)-1-(methylthio)-2-(phenylselanyl)oct-1-enyl]sul-
1
fane (3d): Yield 0.159 g (70%). H NMR (CDCl3, 400 MHz): δ =
7.68–7.65 (m, 2 H), 7.38–7.31 (m, 4 H), 7.23–7.18 (m, 2 H), 7.13–
7.08 (m, 1 H), 2.47 (t, J = 8.0 Hz, 2 H), 2.30 (s, 3 H), 1.27 (quint,
J = 8.0 Hz, 2 H), 1.08 (quint, J = 8.0 Hz, 2 H), 0.98–0.92 (m, 4
H), 0.75 (t, J = 8.0 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 154.1, 136.6, 135.6, 131.4, 129.4, 129.1, 129.0, 128.8, 128.2,
127.0, 126.4, 119.9, 35.7, 31.1, 29.7, 28.5, 22.3, 17.3, 13.9 ppm. MS
(%): m/z (%) = 456 (100), 155 (39), 113 (53), 107 (70), 79 (54).
HRMS: calcd. for C21H25ClS2Se 456.0251; found 456.0256.
(4-Chlorophenyl)[(E)-1-(methylthio)-2-(phenylselanyl)oct-1-enyl]sul-
1
fane (3e): Yield 0.189 g (83%). H NMR (CDCl3, 200 MHz): δ =
7.69–7.65 (m, 2 H), 7.39–7.15 (m, 7 H), 2.47 (t, J = 7.8 Hz, 2 H),
2.40 (s, 3 H), 1.35–1.20 (m, 2 H), 1.13–0.89 (m, 6 H), 0.76 (t, J =
7.8 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): = 152.9, 136.6,
134.8, 131.8, 129.2, 129.1, 129.0, 128.9, 128.8, 120.8, 35.7, 31.1,
29.7, 28.6, 22.3, 17.2, 13.9 ppm. MS (%): m/z (%) = 456 (100), 195
(38), 155 (43), 113 (61), 107 (69), 79 (51). HRMS: calcd. for
C21H25ClS2Se 456.0251; found 456.0248.
2-[(E)-1-(Methylthio)-2-(phenylselanyl)oct-1-enylthio]pyridine (3f):
1
Yield 0.152 g (72%). H NMR (CDCl3, 400 MHz): δ = 8.43 (dd, J
= 5.0 Hz, J = 2.0 Hz, 1 H), 7.69–7.66 (m, 2 H), 7.62–7.55 (m, 2
H), 7.38–7.31 (m, 3 H), 7.20 (d, J = 8.0 Hz, 1 H), 7.04– 7.01 (m, 1
H), 2.48 (t, J = 8.0 Hz, 2 H), 2.35 (s, 3 H), 1.26 (quint, J = 8.0 Hz,
Temperatures above room temperature were maintained by use of 2 H), 1.07 (quint, J = 8.0 Hz, 2 H), 0.95–0.89 (m, 4 H), 0.74 (t, J
a mineral oil bath with an electrically heated coil connected to a
Variac controller.
= 8.0 Hz, 3 H) ppm.13C NMR (CDCl3, 100 MHz): δ = 160.1,
154.9, 149.4, 136.6, 136.5, 129.0, 128.7, 121.0, 119.8, 35.7, 31.0,
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F. Manarin, J. A. Roehrs, E. A. Wilhelm, G. Zeni
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29.5, 28.4, 22.2, 17.3, 13.8 ppm. MS (%): m/z (%) = 266 (100), 181
(10), 67 (7), 112 (10). HRMS: calcd. for C20H25NS2Se 423.0594;
found 423.0591.
(%): m/z (%) = 314 (100), 229 (15), 218 (18), 149 (18), 112 (15), 78
(25). HRMS: calcd. for C20H25NSSe2 471,0038; found 471.0043.
2-[(Z)-1-(Methylselanyl)-2-(phenylselanyl)oct-1-enylthio]-1,3-benzo-
1
2-[(E)-(1-Methylthio)-2-(phenylselanyl)oct-1-enylthio]-1,3-benzox-
xazole (3m): Yield 0.204 g (80%). H NMR (CDCl3, 400 MHz): δ
1
azole (3g): Yield 0.162 g (70%). H NMR (CDCl3, 400 MHz): δ =
= 7.69–7.65 (m, 3 H), 7.49–7.47 (m, 1 H), 7.37–7.32 (m, 3 H), 7.30–
7.27 (m, 2 H), 2.55 (t, J = 7.8 Hz, 2 H), 2.35 (s, 3 H), 1.36 (quint,
J = 7.8 Hz, 2 H), 1.09 (quint, J = 7.8 Hz, 2 H), 1.01–0.97 (m, 4
H), 0.75 (t, J = 7.8 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 162.4, 158.1, 151.9, 142.0, 135.9, 129.6, 129.2, 128.7, 124.3,
124.2, 119.1, 110.0, 109.4, 36.7, 31.1, 29.2, 28.4, 22.2, 13.8,
9.7 ppm. MS (%): m/z (%) = 354 (100), 152 (17), 115 (15), 107 (18),
91 (14), 79 (25). HRMS: calcd. for C22H25NOSSe2 510.9987; found
510.9991.
7.70–7.64 (m, 3 H), 7.49–7.47 (m, 1 H), 7.39–7.27 (m, 5 H), 2.51
(t, J = 7.8 Hz, 2 H), 2.44 (s, 3 H), 1.31 (quint, J = 7.8 Hz, 2 H),
1.08 (quint, J = 7.8 Hz, 2 H), 0.97–0.94 (m, 4 H), 0.74 (t, J =
7.8 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 162.0, 158.8,
152.0, 142.0, 136.7, 136.3, 129.1, 128.9, 124.3, 119.1, 114.9, 110.0,
36.0, 31.0, 29.3, 28.5, 22.2, 17.6, 13.8 ppm. MS (%): m/z (%) = 308
(11), 306 (100), 152 (7), 107 (7), 79 (13). HRMS: calcd. for C22H25
NOS2Se 463.0543; found 463.0547.
5-[(E)-1-(Methylthio)-2-(phenylselanyl)oct-1-enylthio]-1,3,4-thiadi-
azol-2-amine (3h): Yield 0.133 g (60 %). 1H NMR (CDCl3,
400 MHz): δ = 7.65–7.63 (m, 2 H), 7.42–7.32 (m, 3 H), 5.20 (s, 2
H), 2.49 (t, J = 8.0 Hz, 2 H), 2.42 (s, 3 H), 1.29 (quint, J = 8.0 Hz,
2 H), 1.13 (quint, J = 8.0 Hz, 2 H), 1.04–0.94 (m, 4 H), 0.78 (t, J
= 8.0 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 170.1,
155.6, 136.7, 136.4, 129.1, 129.0, 128.9, 119.4, 35.8, 31.1, 29.6, 28.6,
22.3, 17.6, 13.8 ppm. MS (%): m/z (%) = 288 (100), 155 (7), 115
(9), 79 (12), 77 (10). HRMS: calcd. for C17H23N3S3Se 445.0219;
found 445.0224.
5-[(Z)-1-(Methylselanyl)-2-(phenylselanyl)oct-1-enylthio]-1,3,4-thia-
diazol-2-amine (3n): Yield 0.135 g (55 %). 1H NMR (CDCl3,
400 MHz): δ = 7.65–7.60 (m, 2 H), 7.41–7.31 (m, 3 H), 5.68 (s, 2
H), 2.49 (t, J = 8.0 Hz, 2 H), 2.42 (s, 3 H), 1.32–1.25 (m, 2 H),
1.16–1.11 (m, 2 H), 1.03–0.94 (m, 4 H), 0.78 (t, J = 8.0 Hz, 3 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 155.6, 136.7, 136.5, 129.2,
128.9, 119.9, 35.9, 31.2, 29.6, 28.6, 22.3, 17.6, 13.8 ppm. MS (%):
m/z (%) = 288 (100), 227 (5), 155 (7), 115 (9), 85 (11), 79 (12).
HRMS: calcd. for C17H23N3S2Se2 492.9664; found 492.9669.
Benzyl[(Z)-1-(methylselanyl)-2-(phenylselanyl)oct-1-enyl]sulfane
(3o): Yield 0.181 g (75%). H NMR (CDCl3, 400 MHz): δ = 7.46–
2-[(E)-1-(Methylthio)-2-(phenylselanyl)oct-1-enylthio]ethanol (3i):
Yield 0.068 g (35%). H NMR (CDCl3, 400 MHz): δ = 7.63–7.60
1
1
7.43 (m, 2 H), 7.28–7.22 (m, 7 H), 3.89 (s, 2 H), 2.29 (s, 3 H), 2.22
(t, J = 7.8 Hz, 2 H), 1.11 (quint, J = 7.8 Hz, 2 H), 1.06–1.00 (m, 2
H), 0.98–0.93 (m, 2 H), 0.91–0.86 (m, 2 H), 0.78 (t, J = 7.8 Hz, 3
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 150.0, 138.0, 135.2,
129.3, 129.0, 128.9, 128.4, 128.3, 128.0, 122.0, 43.2, 40.2, 36.1, 31.2,
29.1, 28.5, 22.3, 13.9, 9.3 ppm. MS (%): m/z (%) = 484 (18), 227
(11), 107 (16), 91 (100), 77 (12). HRMS: calcd. for C22H28SSe2
484.0242; found 484.0238.
(m, 2 H), 7.37–7.27 (m, 3 H), 3.71 (t, J = 6.0 Hz, 2 H), 2.98 (t, J
= 6.0 Hz, 2 H), 2.43 (t, J = 6.0 Hz, 2 H), 2.36 (s, 3 H), 2.00 (s, 1
H), 1.25 (quint, J = 6.0 Hz, 2 H), 1.14 (quint, J = 6.0 Hz, 2 H),
1.05–0.94 (m, 4 H), 0.79 (t, J = 6.0 Hz, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 150.3, 136.7, 136.6, 128.9, 128.6, 127.8,
61.0, 36.8, 35.3, 31.2, 29.3, 28.6, 22.3, 17.2, 13.9 ppm. MS (%): m/z
(%) = 390 (100), 192 (29), 155 (26), 115 (46), 109 (52), 79 (56).
HRMS: calcd. for C17H26OS2Se 390.0590; found 390.0586.
(4-Chlorobenzyl)[(Z)-1-(methylselanyl)-2-(phenylselanyl)oct-1-enyl]-
sulfane (3p): Yield 0.209 g (81%). H NMR (CDCl3, 400 MHz): δ
[(Z)-1-(Methylselanyl)-2-(phenylselanyl)oct-1-enyl](phenyl)sulfane
(3j): Yield 0.152 g (65%). H NMR (CDCl3, 400 MHz): δ = 7.64–
1
1
= 7.45–7.43 (m, 2 H), 7.30–7.20 (m, 7 H), 3.84 (s, 2 H), 2.29 (s, 3
H), 2.18 (t, J = 7.8 Hz, 2 H), 1.12 (quint, J = 7.8 Hz, 2 H), 1.04–
0.96 (m, 4 H), 0.90–0.84 (m, 2 H), 0.79 (t, J = 7.8 Hz, 3 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 150.8, 136.7, 135.3, 132.7, 130.6,
130.4, 129.0, 128.4, 128.1, 121.0, 39.3, 35.9, 31.2, 29.2, 28.5, 22.3,
13.9, 9.3 ppm. MS (%): m/z (%) = 516 (18), 195 (44), 115 (100),
107 (90), 77 (78), 67 (95). HRMS: calcd. for C22H27ClSSe2
517.9852; found 517.9856.
7.62 (m, 2 H), 7.35–7.27 (m, 8 H), 2.53 (t, J = 7.8 Hz, 2 H), 2.14
(s, 3 H), 1.36 (quint, J = 7.8 Hz, 2 H), 1.13 (quint, J = 7.8 Hz, 2
H), 1.05–0.99 (m, 4 H), 0.77 (t, J = 7.8 Hz, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 151.2, 137.0, 135.4, 129.9, 129.1, 128.9,
128.3, 127.1, 125.7, 36.8, 31.2, 29.5, 28.6, 22.3, 13.9, 9.5 ppm. MS
(%): m/z (%) = 363 (100), 318 (63), 281 (68), 206 (42), 129 (58), 77
(39). HRMS: calcd. for C21H26SSe2 470.0086; found 470.0412.
(2-Chlorophenyl)[(Z)-1-(methylselanyl)-2-(phenylselanyl)oct-1-enyl]-
1
sulfane (3k): Yield 0.151 g (60%). H NMR (CDCl3, 400 MHz): δ
Dodecyl[(Z)-1-(methylselanyl)-2-(phenylselanyl)oct-1-enyl]sulfane
1
= 7.65–7.63 (m, 2 H), 7.37–7.31 (m, 4 H), 7.23–7.22 (m, 2 H), 7.14–
7.01 (m, 1 H), 2.50 (t, J = 7.8 Hz, 2 H), 2.14 (s, 3 H), 1.34 (quint,
J = 7.8 Hz, 2 H), 1.12 (quint, J = 7.8 Hz, 2 H), 1.03–0.99 (m, 4
H), 0.77 (t, J = 7.8 Hz, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 153.1, 136.2, 135.6, 131.0, 129.5, 129.2, 128.5, 127.7, 127.1,
126.4, 117.2, 36.8, 31.2, 29.5, 28.5, 22.3, 13.9, 9.5 ppm. MS (%):
m/z (%) = 504 (85), 252 (41), 181 (49), 115 (56), 107 (100), 79 (71).
HRMS: calcd. for C21H25ClSSe2 503.9696; found 503.9691.
(3q): Yield 0.112 g (40%). H NMR (CDCl3, 400 MHz): δ = 7.55–
7.52 (m, 2 H), 7.32–7.29 (m, 3 H), 3.74 (t, J = 7.0 Hz, 2 H), 2.32
(t, J = 7.0 Hz, 2 H), 2.29 (s, 3 H), 1.85 (t, J = 7.0 Hz, 2 H), 1.40
(quint, J = 7.0 Hz, 2 H), 1.31–1.17 (m, 11 H), 1.11 (quint, J =
7.0 Hz, 4 H), 0.88 (t, J = 7.0 Hz, 2 H), 0.82 (t, J = 7.0 Hz, 3 H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 143.8, 135.3, 134.7, 129.2,
129.0, 128.2, 43.7, 36.3, 35.9, 31.8, 31.3, 29.5, 28.8, 28.6, 28.5, 27.8,
25.6, 22.6, 22.4, 14.9, 14.0, 13.9 ppm. MS (%): m/z (%) = 488 (13),
265 (30), 195 (33), 107 (61), 79 (65), 67 (100). HRMS: calcd. for
C27H46SSe2 562.1651; found 562.1655.
2-[(Z)-1-(Methylselanyl)-2-(phenylselanyl)oct-1-enylthio]pyridine
(3l): Yield 0.141 g (60%). 1H NMR (CDCl3, 400 MHz): δ = 8.43
(dd, J = 5.0 Hz, J = 2.0 Hz, 1 H), 7.66–7.63 (m, 2 H), 7.58 (td, J
= 8.0 Hz, J = 1.5 Hz 1 H), 7.36–7.3 (m, 2 H), 7.24 (t, J = 8.0 Hz,
1 H), 7.06–7.02 (m, 1 H), 2.52 (t, J = 8.0 Hz, 2 H), 2.20 (s, 3 H),
1.33 (quint, J = 8.0 Hz, 2 H), 1.10 (quint, J = 8.0 Hz, 2 H), 1.02–
Supporting Information (see also the footnote on the first page of
this article): Spectroscopic data for 3a–q.
CCDC-695258 (for 3a) and -695259 (for 3b) contain the supple-
0.96 (m, 4 H), 0.76 (t, J = 8.0 Hz, 3 H) ppm.13C NMR (CDCl3, mentary crystallographic data for this paper. These data can be
100 MHz): δ = 160.2, 153.6, 149.6, 136.7, 135.5, 129.6, 129.2, 128.5,
120.8, 119.9, 116.5, 36.9, 31.2, 29.5, 28.5, 22.3, 13.9, 9.7 ppm. MS
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
4464
www.eurjoc.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 4460–4465

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Acknowledgments
[5]
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We are grateful to the Conselho Nacional de Desenvolvimento
Científico e Tecnológico, the Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior (SAUX), and the Fundação de Amparo
à Pesquisa do Estado do Rio Grande do Sul for a fellowship and
financial support.
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Received: May 21, 2008
Published Online: July 25, 2008
Eur. J. Org. Chem. 2008, 4460–4465
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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