Copper Nanoparticle Catalyzed Formation of C-S Bonds through Activation of S-S and C-H Bonds: An Easy Route to Alkynyl Sulfides

Article abstract of DOI:10.1055/s-0035-1560458

An efficient method for copper nanoparticle catalyzed ligand-free S-C_sp bond formation was developed by using dimethyl sulfoxide as the solvent, a base, and molecular oxygen as a green oxidant. This study provides a new catalytic route for the

Full text of DOI:10.1055/s-0035-1560458

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2015, 47, 3741–3745
paper
3741
B. Mohan et al.
Paper
Synthesis
Copper Nanoparticle Catalyzed Formation of C–S Bonds through
Activation of S–S and C–H Bonds: An Easy Route to Alkynyl
Sulfides
Balaji Mohan
Sori Hwang
Csp–S or Se, Te bond formation
Cu NPs, O2, base
PhSSPh
PhS
(CH2)9Me
Hyunje Woo
Kang Hyun Park*
Cu NPs, air, base
PhSeSePh
H
(CH2)9Me
PhSe
PhTe
(CH2)9Me
(CH2)9Me
Department of Chemistry, Pusan National University,
Busan, 609735, South Korea
chemistry@pusan.ac.kr
TM free, air, base
PhTeTePh
C–H activation
low catalyst loading, ligand-free, large scale,
substrate scope
Received: 10.05.2015
Accepted after revision: 16.07.2015
Published online: 21.08.2015
es that are compatible with various demanding substitu-
ents, operate under mild reaction conditions, and that are
environmentally benign are continually being sought. Un-
fortunately, most of the existing synthetic protocols that are
widely applicable require the use of selenides and tellu-
rides.10–20 Therefore, new synthetic strategies for the pro-
duction of alkynyl sulfides from simple starting materials
with a sustainable and atom-economical approach are be-
ing developed. Moreover, the present stringent environ-
mental standards have forced researchers to develop alter-
native green protocols that involve the use of molecular ox-
ygen as a primary oxidant in the presence of a catalyst.
Recently, Robert and co-workers reported the copper
salt catalyzed cross-dehydrogenative coupling of terminal
alkynes with different functionalities in good yields.21
However, they used a high loading of Cu and an environ-
mentally unfriendly reagent, thiophenol. Schneider et al.
developed an approach that involved the use of 10 mol% in-
dium for the synthesis of chalcogenoacetylenes in anhy-
drous DMSO.17 The Bieber research group used CuI as cata-
lyst to couple diaryldichalcogens and terminal alkynes to
afford organochalcogeno acetylenes.20 Most of the afore-
mentioned techniques suffer from a high loading of cata-
lysts and limited substrate compatibility (aryl acetylenes),
and they are not suitable for large-scale applications.
DOI: 10.1055/s-0035-1560458; Art ID: ss-2015-f0303-op
Abstract An efficient method for copper nanoparticle catalyzed li-
gand-free S–Csp bond formation was developed by using dimethyl sulf-
oxide as the solvent, a base, and molecular oxygen as a green oxidant.
This study provides a new catalytic route for the production of alkynyl
sulfides through dual activation of S–S and C–H bonds. A wide range of
alkynyl sulfides were synthesized on a large scale with a low catalyst
loading (0.5 mol% Cu). This synthetic methodology could also be ex-
tended to selenides, whereas tellurides underwent analogous reactions
in the absence of a catalyst.
Key words alkynes, copper, cross-coupling, chalcogenides, nanoca-
talysis
Alkynyl sulfides are readily available precursors for the
synthesis of a number of systems, including: vinylic sulfides
by the hydroboration of thioacetylene,1,2 substituted
alkynes,3,4 2-chalcogene-1-halonaphthalenes by [4+2] cy-
cloaddition annulation,5 and zirconated vinyl chalco-
genides.6 Sulfur-substituted 1,2,3-triazoles7 are herbicides
with antifungal activity, and ThioClickFerrophos has been
used as a ligand8 in the preparation of endo-4-acyl pyrroli-
dines with high enantioselectivity (Figure 1).
Nanoparticles (NPs) have been used to catalyze a wide
range of reactions (nanocatalysis) in the past decade under
both homogeneous and heterogeneous conditions.22–25 Be-
cause NPs have a large surface-to-volume ratio compared
with that of bulk materials, they are attractive candidates as
catalysts. Thus, transition-metal NPs have been widely used
as catalysts in various organic transformations,26–28 as evi-
dent from the growing number of publications on this top-
ic, indicating the importance of nanocatalysis. The prepara-
tion of efficient NPs without surfactants under mild reac-
tion conditions is thus clearly important. In this context,
CO2Et
Me
N
Fe
Ph2P
Cl
N
N
N
S
N
R
OH
N
EtS
Figure 1 Antifungal drug (left) and ThioClickFerrophos (right)
Recently, thioalkynes were effectively utilized as start-
ing material for the synthesis of thio-substituted 1,2,3-tri-
azoles.9 With increasing demand for thioalkynes because of
their vast range of applications, simple synthetic approach-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 3741–3745

3742
B. Mohan et al.
Paper
Synthesis
transition-metal NP-catalyzed cross-coupling reactions
may also provide a good platform to synthesize more com-
plex molecules.
21). Therefore, the optimized reaction conditions for the
cross-coupling of diphenyl disulfide and terminal alkynes
were established as: diphenyl disulfide (1 mmol), 0.5 mol%
Cu NPs, Na2CO3 (2.2 equiv), terminal alkyne (2.2 equiv), and
O2 (2 atm) in DMSO at 70 °C for 12 h. The product 3aa was
characterized by GC-MS, HRMS, and by 1H and 13C NMR
spectral analyses.
With the optimized reaction conditions established, the
substrate scope and limitations of the coupling reaction
were investigated; the results are summarized in Table 2.
All the experiments were conducted with 500 mg diphenyl
disulfide (1a). In general, the reaction proceeded well and
afforded the desired alkynyl sulfides 3 in moderate yields.
An assortment of long-chain terminal alkynes 2b–f [1-tet-
radecyne (2b), 1-dodecyne (2c), 1-nonyne (2d), 1-heptyne
(2e), and 1-pentyne (2f)] afforded the corresponding alkyn-
ylphenyl sulfides in good to moderate yields (entries 1–5).
Unfortunately, in the case of 1-ethynylcyclohexene (2g), no
cross-coupling product was observed under the standard
conditions.
In a continuation of our efforts to develop copper cata-
lysts29,30 and chalcogen chemistry,31,32 we report here the
efficient use of a copper nanoparticle catalyst in the cross-
coupling reaction of an environmentally friendly reagent
diphenyl disulfide with terminal alkynes. To investigate the
copper nanoparticle-catalyzed alkynylation reaction, di-
phenyl disulfide (1a) and 1-decyne (2a) were selected as
representative substrates for initial screening (Scheme 1).
Dimethyl sulfoxide (DMSO) was used as solvent, and other
parameters such as temperature, time, base, and additive
were varied systematically (Table 1).
S
S
1a
S
(CH2)7Me
Cu NPs
+
DMSO, base
additive
70 °C, 12 h
H
(CH2)7Me
2a
Table 1 Optimization of the Cu NP Catalyzed Cross-Coupling Reaction
of 1a with 2a
3aa
Scheme 1 Cross-coupling of diphenyl disulfide and 1-decyne
Entry
Cat. (mol%) Base
Additive
Yield (%)b
1
2
0.5
2
Na2CO3
–
37
40
39c
ND
30
1
The reaction of 1a with Cu NPs (0.5 mol%), base (2.2
equiv), and alkyne 2a (2.2 equiv) in DMSO (4 mL) at 70 °C
for 12 h afforded the corresponding product in 37% yield
(Table 1, entry 1). Increasing the amount of catalyst from
0.5 to 2 mol% increased the yield only slightly (entry 2). In-
creasing the reaction time also produced similar results
(entry 3). The reaction did not proceed at all in the absence
of the catalyst (entry 4). The use of a diverse range of bases
did not improve the yield (entries 5–9). Further investiga-
tions revealed that the use of zinc dust as an additive did
not afford any cross-coupled product, whereas the addition
of manganese powder minimized the yield (entries 10 and
11). The use of ligands such as bipyridyl, phenanthroline,
and TMEDA failed to afford satisfactory results (entries 12–
14). Running the reaction under oxygen (1 atm) afforded
the cross-coupled product in 38% yield, whereas reaction
under argon (1 atm) led to complete recovery of the start-
ing materials (entries 15 and 16), which confirms the re-
quired use of oxidant to promote the cross-coupling. Sur-
prisingly, the reaction occurred efficiently and afforded the
desired cross-coupled product 3aa in 77% yield under 2 atm
oxygen. Thus, O2 was essential as the oxidant for good con-
version. An increase in the catalyst quantity provided al-
most the same results (entry 18). No significant improve-
ment in yield was observed when 3 atm oxygen was used
under identical conditions. Moreover, increasing the scale
of the reaction (from 100 mg 1a to 500 mg) did not reduce
the yield (entry 20). Performing the reaction at room tem-
perature for 24 hours resulted in a diminished yield (entry
Na2CO3
Na2CO3
Na2CO3
K2CO3
–
3
0.5
–
–
4
–
5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
–
6
Cs2CO3
Ag2CO3
Li2CO3
–
7
–
4
8
–
5
9
K3PO4
–
trace
ND
30
27
2
10
11
12
13
14
15
16
17
18
19
20
21
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
zinc dust
manganese powder
2,2′-bipyridyl
phenanthroline
TMEDA
27
38
ND
77
80
79
76d
12e
O2 (1 atm)
Ar (1 atm)
O2 (2 atm)
O2 (2 atm)
O2 (3 atm)
O2 (2 atm)
O2 (2 atm)
0.5
0.5
0.5
a Reaction conditions: 1a (100 mg, 1 equiv), 2a (2.2 equiv), Cu NP, addi-
tive, base (2.2 equiv), DMSO (4 mL), 12 h, 70 °C.
b Determined by GC-MS analysis (referenced to diphenyl disulfide).
c Reaction for 24 h.
d Scale-up to ca. 500 mg diphenyl disulfide.
e Reaction conducted at r.t.
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Table 2 Cross-Coupling of Diphenyl Disulfide (1a) and Alkynes
S
(CH2)nMe
Cu NPs (0.5 mol%)
S
+
H
(CH2)nMe
S
DMSO, Na2CO3, 70 °C
O2 (2 atm)
2
1a
3
n = 11, 9, 6, 4 or 2
Entry
1
Alkyne
Product
Yield (%)a
S
(CH2)11Me
(CH2)9Me
(CH2)6Me
(CH2)4Me
(CH2)2Me
H
2b
(CH2)11Me
(CH2)9Me
(CH2)6Me
(CH2)4Me
77
61
72
3ab
S
H
2c
2
3
4
5
3ac
S
H
2d
3ad
S
H
2e
63
54
3ae
S
H
2f
(CH2)2Me
3af
S
H
6
ND
2g
3ag
a Determined by GC-MS analysis.
The protocol could also be applied to the reaction of di-
phenyl diselenide with long chain alkyne 1-dodecyne un-
der air (atmospheric air as oxidant) to afford the corre-
sponding cross-coupled product alkynylphenyl selenide
3bc in excellent yield under mild conditions (Scheme 2).
Applying the reaction conditions to diphenyl ditellu-
rides led to the formation of 3cc. In this case, the reaction
proceeded smoothly even in the absence of copper
nanoparticles at room temperature and rendered the prod-
uct alkynylphenyl telluride in 65% yield by utilizing only N-
methyl-2-pyrrolidone (NMP) as solvent and just 10 mol%
Cs2CO3 as base (Scheme 3).
Se
Se
Te
Te
1b
Se
(CH2)9Me
Cu NPs (0.5 mol%)
1c
+
Te
(CH2)9Me
Cs2CO3 (10 mol%)
NMP, r.t., air, 1 d
DMSO, Na2CO3, 70 °C
air, 6 h
+
H
(CH2)9Me
3bc 94%
large scale, no ligand,
low catalyst loading, high yield
H
(CH2)9Me
2c
3cc 65%
large scale, no ligand, no catalyst,
room temperature, high yield
Scheme 2 Cross-coupling of diphenyl diselenide and 1-dodecyne un-
2c
der air
Scheme 3 Cross-coupling of diphenyl ditelluride and 1-dodecyne un-
der air
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Synthesis
Based on existing reports,14,35,36 we hypothesize that the
oxidative addition of Cu(0) to diphenyl disulfide affords in-
termediate II followed by the insertion of II to alkyne in the
presence of base and oxygen to generate intermediate III.
Finally, reductive elimination of III furnishes the corre-
sponding cross-coupled product IV, as illustrated in
Scheme 4.
diluted with Et2O, passed through Celite, washed with H2O, and the
organic extract was dried with anhydrous MgSO4, filtered, and the
solvent was removed under rotary evaporation. The crude product
was analyzed by GC-MS. After analysis, the pure product was isolated
by column chromatography using hexane as eluent.
Synthesis of Alkynyl Selenides
To a Schlenk tube, diphenyl diselenide (1.60 mmol), 1-dodecyne (3.52
mmol), Na2CO3 (3.52 mmol), and DMSO (2 mL) were added, followed
by Cu NPs (0.5 mol%) dispersed after sonication in DMSO (2 mL). The
mixture was stirred at 70 °C for 6 h, then worked up as described for
the sulfides.
ArS
R
IV
ArSSAr
Cu0
I
Synthesis of Alkynyl Tellurides
To a Schlenk tube, diphenyl ditelluride (1.22 mmol), 1-dodecyne (2.68
mmol), Cs2CO3 (10 mol%), and NMP (4 mL) were added and the mix-
ture was stirred at r.t. for 24 h. After the reaction, the mixture was
diluted with Et2O and washed with H2O. The combined organic ex-
tracts were dried with anhydrous MgSO4, filtered, and the solvent
was removed under rotary evaporation. After GC-MS analysis, the
crude product was purified by chromatography on silica gel using
hexane as an eluent to afford the desired product.
ArS
II
SAr
ArS
R
CuII
III
CuII
O2
base
R
H
ArSNa
ArSSAr
Na
C
R
Dec-1-yn-1-yl(phenyl)sulfane (3aa)
Yield: 434 mg (77%); colorless oil.
= copper nanoparticles
1H NMR (300 MHz, CDCl3): δ = 0.88 (t, J = 6.3 Hz, 3 H), 1.27–1.46 (m,
10 H), 1.55–1.65 (m, 2 H), 2.45 (t, J = 6.3 Hz, 2 H), 7.16–7.21 (m, 1 H),
7.29–7.34 (m, 2 H), 7.39–7.42 (m, 2 H).
Scheme 4 Plausible catalytic cycle for Cu NP catalyzed alkynylation of
diphenyl disulfide
13C NMR (75 MHz, CDCl3): δ = 14.1, 20.3, 22.7, 28.6, 28.9, 29.1, 29.3,
29.5, 29.6, 31.9, 64.4, 100.1, 125.7, 126.0, 129.0, 133.8.
HRMS (EI): m/z calcd for C16H22S: 246.1442; found: 246.1442.
In summary, we have disclosed an efficient catalytic
system that activates S–S and C–H bonds efficiently and
that leads to the formation of S–Csp bonds. This methodolo-
gy permits the preparation of challenging compounds and
proceeds in the absence of ligands under mild conditions
with inexpensive and green oxidant with low catalyst load-
ing. Remarkably, the present technique is also compatible
for use with diphenyl diselenides, and analogous tellurides
proceed through a cesium effect.
Tetradec-1-yn-1-yl(phenyl)sulfane (3ab)
Yield: 533 mg (77%); colorless oil.
1H NMR (300 MHz, CDCl3): δ = 0.91 (t, J = 6.3 Hz, 3 H), 1.29–1.67 (m,
20 H), 2.47 (t, J = 7.2 Hz, 2 H), 7.18–7.23 (m, 1 H), 7.31–7.44 (m, 4 H).
13C NMR (75 MHz, CDCl3): δ = 14.2, 20.4, 22.8, 28.8, 29.0, 29.2, 29.5,
29.7, 29.8, 32.0, 64.7, 100.2, 125.8, 126.2, 129.2, 133.9.
HRMS (EI): m/z calcd for C20H30S: 302.2068; found: 302.2068.
Dodec-1-yn-1-yl(phenyl)sulfane (3ac)
Yield: 383 mg (61%); colorless oil.
All starting materials were purchased from Aldrich Chemical Co., TCI,
or Strem Chemical Co. and used as received. Cesium carbonate was
purchased from Acros Organics (Cat. No. 192041000). Reaction prod-
ucts were analyzed by GC-MS (Shimadzu-QP2010 SE), and by 1H and
13C NMR spectroscopy (Varian Mercury Plus, 300 MHz). Chemical
shift values are recorded as parts per million (ppm) relative to te-
tramethylsilane as internal standard, unless otherwise indicated;
coupling constant values are in Hz. HRMS analysis was carried out at
the Korea Basic Science Institute. The copper nanoparticle catalysts
were synthesized as described in our previous publication.33
1H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 6.3 Hz, 3 H), 1.29–1.46 (m,
14 H), 1.56–1.65 (m, 2 H), 2.45 (t, J = 6.9 Hz, 2 H), 7.16–7.21 (m, 1 H),
7.29–7.34 (m, 2 H), 7.39–7.42 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 14.1, 20.3, 22.6, 28.6, 28.9, 29.1, 29.2,
31.8, 64.4, 100.1, 125.7, 126.0, 129.0, 133.7.
HRMS (EI): m/z calcd for C18H26S: 274.1755; found: 274.1756.
Non-1-yn-1-yl(phenyl)sulfane (3ad)
Yield: 383 mg (72%); yellow oil.
Alkynylation of Diphenyl Sisulfides; General Procedure
1H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 6.6 Hz, 3 H), 1.29–1.46 (m,
8 H), 1.55–1.65 (m, 2 H), 2.44 (t, J = 6.9 Hz, 2 H), 7.16–7.21 (m, 1 H),
7.29–7.34 (m, 2 H), 7.38–7.42 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 14.1, 20.3, 22.6, 28.7, 28.8, 28.9, 31.8,
64.5, 100.1, 125.7, 126.0, 133.8.
An autoclave was charged with diphenyl disulfide (1 equiv), alkyne
(2.2 equiv), base (2.2 equiv), catalyst (0.5 mol%), DMSO (4 mL), and a
magnetic stirring bar. The autoclave was purged and filled with O2 to
the stated gauge pressure (2 atm), and the reaction mixture was
stirred at 70 °C for 12 h. After the reaction, the reaction mixture was
HRMS (EI): m/z calcd for C15H20S: 232.1286; found: 232.1286.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 3741–3745

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Synthesis
Hept-1-yn-1-yl(phenyl)sulfane (3ae)
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Yield: 294 mg (63%); colorless oil.
1H NMR (300 MHz, CDCl3): δ = 0.92 (t, J = 7.2 Hz, 3 H), 1.31–1.47 (m,
4 H), 1.56–1.66 (m, 2 H), 2.45 (t, J = 7.2 Hz, 2 H), 7.17–7.22 (m, 1 H),
7.29–7.35 (m, 2 H), 7.38–7.43 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 14.0, 20.3, 22.2, 28.3, 31.0, 64.5, 100.2,
125.7, 126.1, 129.0, 133.8.
HRMS (EI): m/z calcd for C13H16S: 204.0973; found: 204.0973.
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Pent-1-yn-1-yl(phenyl)sulfane (3af)
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B.; Braga, A. L. Tetrahedron 2014, 70, 3349.
Yield: 218 mg (54%); yellow oil.
1H NMR (300 MHz, CDCl3): δ = 1.04 (t, J = 6.9 Hz, 3 H), 1.57–1.68 (m,
2 H), 2.44 (t, J = 7.2 Hz, 2 H), 7.17–7.22 (m, 1 H), 7.29–7.34 (m, 2 H),
7.39–7.43 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 13.6, 22.1, 22.3, 64.6, 99.9, 125.7, 126.0,
129.0, 133.7.
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Perin, G. Tetrahedron 2012, 68, 10414.
HRMS (EI): m/z calcd for C11H12S: 176.0660; found: 176.0660.
Dodec-1-yn-1-yl(phenyl)selane (3bc)
Yield: 485 mg (94%); yellow oil.
1H NMR (300 MHz, CDCl3): δ = 0.88 (t, J = 6.3 Hz, 3 H), 1.26–1.45 (m,
14 H), 1.54–1.64 (m, 2 H), 2.45 (t, J = 14.1 Hz, 2 H), 7.20–7.33 (m, 3 H),
7.49–7.53 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 14.1, 20.6, 22.7, 28.7, 28.9, 29.1, 29.3,
29.5, 29.6, 31.9, 57.3, 104.8, 126.7, 128.4, 128.5, 129.3.
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HRMS (EI): m/z calcd for C18H26Se: 322.1200; found: 322.1200.
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Yield: 294 mg (65%); yellow oil.
1H NMR (300 MHz, CDCl3): δ = 0.88 (t, J = 6.3 Hz, 3 H), 1.27–1.43 (m,
14 H), 1.52–1.61 (m, 2 H), 2.57 (t, J = 6.9 Hz, 2 H), 7.22–7.27 (m, 3 H),
7.65–7.68 (m, 2 H).
13C NMR (75 MHz, CDCl3): δ = 14.1, 21.1, 22.7, 28.8, 28.9, 29.1, 29.3,
29.5, 29.6, 31.9, 34.6, 113.1, 116.2, 127.6, 129.2, 129.6, 134.7, 137.6.
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Acknowledgment
This research was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Science, ICT
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 3741–3745