Addition of diaryl disulfides to terminal alkynes catalysed by an MCM-41-supported bidentate phosphine palladium(0) complex

Article abstract of DOI:10.3184/030823409X12526892025829

A variety of (Z)-1,2-bis(arylthio)-substituted alkenes have been conveniently synthesised in high yields by the stereoselective addition of diaryl disulfides to terminal alkynes catalysed by an MCM-41-supported bidentate phosphine palladium(0) complex. Th

Full text of DOI:10.3184/030823409X12526892025829

616 RESEARCH PAPER
OCTOBER, 616–618
JOURNAL OF CHEMICAL RESEARCH 2009
Addition of diaryl disulfides to terminal alkynes catalysed by an
MCM-41-supported bidentate phosphine palladium(0) complex
Jianying Lia,b, Jun Liua and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
bDepartment of Chemistry, Jingdezhen Comprehensive College, Jingdezhen 333000, P. R. China
A variety of (Z)-1,2-bis(arylthio)-substituted alkenes have been conveniently synthesised in high yields by the
stereoselective addition of diaryl disulfides to terminal alkynes catalysed by an MCM-41-supported bidentate
phosphine palladium(0) complex. This polymeric palladium catalyst can be recovered and reused many times
without any loss of activity.
Keywords: vinylic sulfide, supported catalyst, palladium, MCM-41, catalysis
The development of environmentally friendly synthetic
procedures has become a major concern throughout the
chemical industry due to continuing depletion of natural
resources and growing environmental awareness.1-4 The high
costs of transition-metal catalysts coupled with toxic effects
associated with many transition metals has led to an increased
interest in immobilising catalysts onto supports. This class
of supported reagents can facilitate both the isolation and
recycling of the catalysts by simple filtration, thus providing
environmentally cleaner processes.5,6
that MCM-41 support has an extremely high surface area and
the catalytic palladium species is anchored on the inner surface
of the mesopore of the MCM-41 support, we expect that MCM-
41-supported palladium catalysts will exhibit high activity
and good reusability. To date, a few palladium complexes
on functionalised MCM-41 supports have been prepared and
successfully used in organic reactions.29-32 Very recently,
we have reported the synthesis of the MCM-41-supported
bidentate phosphine palladium(0) complex [abbreviated as
MCM-41-2P-Pd(0)] and found that this complex is a highly
active and recyclable catalyst for Sonogashira reactions of
aryl halides.33 However, to the best of our knowledge, there
has been no general study reported of the addition of diaryl
disulfides to terminal alkynes catalysed by an MCM-41-
supported palladium complex. We now report that a variety of
(Z)-1,2-bis(arylthio)-substituted alkenes can be conveniently
synthesised in high yields by the stereoselective addition of
diaryl disulfides to terminal alkynes in the presence of a sub-
stoichiometric amount of the MCM-41-supported bidentate
phosphine palladium(0) complex [MCM-41-2P-Pd(0)].
Catalytic diaryl disulfide addition to terminal alkynes was
discovered by Ogawa, Sonoda and coworkers.7-9 The products
of the addition reaction are of much practical interest in organic
chemistry10-12 and materials science.13,14 The mechanism
of this catalytic reaction has been extensively studied and
proceeds via: (1) oxidative addition of the S–S bond to Pd(0);
(2) the stereoselective insertion of acetylenes into the Pd–S
bond and (3) C–S reductive elimination.7-9 Recently,Ananikov
and Beletskaya reported the solvent-free palladium-catalysed
addition of diaryl disulfides to terminal alkynes15 and
palladium-catalysed addition of diaryl disulfides to terminal
alkynes under microwave irradiation.16 The reaction is
usually catalysed by homogeneous palladium complexes such
as Pd(PPh3)4. However, the homogeneous palladium catalysts
are sensitive to air and moisture and cannot be recovered
and reused. We reported that palladium-catalysed addition of
diaryl disulfides to terminal alkynes can proceed smoothly in
a room temperature ionic liquid ([bmim][PF6]); high yields
and stereoselectivity were observed for various alkynes and
the ionic liquid and the palladium catalyst can be recycled
four times.17 Recently, Xu and coworkers described caesium
hydroxide-catalysed addition of diaryl disulfides to terminal
alkynes with high stereoselectivity and good yields.18,19 From
the standpoint of environmentally benign organic synthesis,
development of immobilised palladium catalysts is challenging
and important.20-22 In an ideal system, they can be recovered
from the reaction mixture by simple filtration and re-used
indefinitely, and contamination of products by palladium
is prevented. Beletskaya and coworkers have reported the
first example of a polymer-supported palladium catalyst for
stereoselective S-S bond addition to terminal alkynes.23
MCM-41-2P-Pd(0) was prepared according to our previous
procedure.33 The phosphine and palladium contents were
1.15 and 0.52 mmolg-1, respectively. Initially, to determine
the optimum conditions, the addition of diphenyl disulfide
to hex-1-yne (1.5 equiv.) was examined under different
conditions. We found that, the addition reaction in benzene
or toluene in the presence of 2 mol% MCM-41-2P-Pd(0) at
70°C did not occur. However, the same reaction in toluene
at 140°C under sealed-tube conditions proceeded smoothly
and stereoselectively to give (Z)-1,2-bis(phenylthio)hex-1-
ene (3a) in 90% yield. The scope of the reaction was studied
for different alkynes and diaryl disulfides (Scheme 1).
The experimental results are summarised in Table 1. As shown
in Table 1, the addition reactions of diaryl disulfides to a
variety of terminal alkynes proceeded very smoothly to give
the corresponding (Z)-1,2-bis(arylthio)-1- alkenes 3a–k in high
yields with high stereoselectivity (Z/E>99:1) after 2 hours.
1
The purity of the products 3 was established by H NMR,
13C NMR and elemental analysis. The Z-configuration of the
double bond of products 3 was determined by a 2D NOESY
experiment. For example, irradiation of the methylene triplet
at d 2.23 of compound 3a resulted in a 16% enhancement
of the signal at d 6.54 (vinyl singlet) and irradiation of the
methylene triplet at d 2.50 of compound 3k resulted in a
18% enhancement of the signal at d 6.73 (vinyl singlet). The
NOE results indicate that compounds 3a and 3k have the
expected Z-configuration. The reaction can tolerate a number
of functional groups such as hydroxyl, amino, trimethylsilyl,
and methoxyl.
Recent developments on the mesoporous material MCM-
41 provided a new possible candidate for a solid support for
immobilisation of homogeneous catalysts.24 MCM-41 has a
regular pore diameter of ca.5 nm and a specific surface area
> 700 m2 g-1.25 Its large pore size allows passage of large
molecules such as organic reactants and metal complexes
through the pores to reach to the surface of the channel.26-28 It
is generally believed that high surface area of heterogeneous
catalysts results in high catalytic activity. Considering the fact
The MCM-41-2P-Pd(0) catalyst can be easily recovered by
simple filtration. We also investigated the possibility of reusing
of the catalyst by using the addition reaction of diphenyl
* Correspondent. E-mail: caimzhong@163.com

JOURNAL OF CHEMICAL RESEARCH 2009 617
R
2 mol% MCM-41-2P-Pd(0)
R
+
Ar2S2
o
toluene, 140 C, 2 h
SAr
ArS
2
1
3
OSiMe3
PPh2
Pd
PPh2
O
Si(CH2)3N
MCM-41-2P-Pd(0) =
O
OEt
Scheme 1
(2 ¥ 5 mL) and reused in the next run. The combined organic
solutions were concentrated under reduced pressure, and the residue
was purified by preparative TLC on silica gel.
disulfide to hex-1-yne (1.5 equiv.). In general, the continuous
recycling of resin-supported palladium catalysts is difficult
owing to leaching of the palladium species from the polymer
supports, which often reduces their activity within a five-
recycle run. However, when 2 mol% of MCM-41-2P-Pd(0)
was used in five consecutive runs for the addition of diphenyl
disulfide to hex-1-yne (1.5 equiv.), (Z)-1,2-bis(phenylthio)-1-
hexene (3a) was formed in 90, 89, 90, 90 and 88% yields,
respectively. The high stability and excellent reusability of the
catalyst may result from the chelating action of the bidentate
phosphine ligand on palladium and the mesoporous structure
of the MCM-41 support. The result is important from a
practical point of view.
In conclusion, we have described the stereoselective
addition of diaryl disulfides to terminal alkynes catalysed
by an MCM-41-supported bidentate phosphine palladium(0)
complex. High yields and stereoselectivities were observed for
various alkynes. Easy product isolation and catalyst recycling
are important advantages of the developed methodology.
(Z)-1,2-Diphenylthiohex-1-ene (3a): Oil. IR (neat): n (cm-1) 3059,
2957, 2928, 1582, 1478, 1439, 1024, 739, 690; 1H NMR (400 MHz,
CDCl3): d 7.41–7.20 (m, 10H), 6.54 (s, 1H), 2.23 (t, J = 7.4 Hz, 2H),
1.50–1.42 (m, 2H), 1.26–1.20 (m, 2H), 0.82 (t, J = 7.4 Hz, 3H); 13
C
NMR (100 MHz, CDCl3): d 135.9, 134.3, 133.8, 130.5, 129.7, 129.1,
129.0, 128.9, 126.8, 126.7, 36.8, 30.7, 21.9, 13.8; MS (EI): m/z 300
(M+, 97), 147 (100); Anal. Calcd for C18H20S2: C, 71.95; H, 6.71.
Found: C, 71.67; H, 6.63%.
(Z)-1,2-Bis[(4-methylphenyl)thio]hex-1-ene (3b): Oil. IR (neat):
n (cm-1) 3020, 2956, 2928, 1564, 1491, 1453, 1401, 1091, 1018, 805;
1H NMR (400 MHz, CDCl3): d 7.33–7.27 (m, 4H), 7.14–7.09 (m,
4H), 6.46 (s, 1H), 2.34 (s, 3H), 2.33 (s, 3H), 2.20 (t, J = 7.4 Hz, 2H),
1.51–1.41 (m, 2H), 1.25–1.19 (m, 2H), 0.83 (t, J = 7.2 Hz, 3H); 13
C
NMR (100 MHz, CDCl3): d 136.9, 134.2, 132.4, 131.1, 130.2, 130.1,
129.9, 129.7, 128.7, 36.6, 30.7, 22.0, 21.2, 21.1, 13.9; MS (EI): m/z
328 (M+, 65), 195 (100); Anal. Calcd for C20H24S2: C, 73.12; H, 7.36.
Found: C, 72.86; H, 7.15%.
(Z)-2,3-Diphenylthioprop-2-en-1-ol (3c)7: Oil. IR (neat): n (cm-1)
3382, 3057, 1716, 1581, 1478, 1439, 1091, 1024, 740, 690; 1H NMR
(400 MHz, CDCl3): d 7.44–7.21 (m, 10H), 7.03 (s, 1H), 4.14 (s, 2H),
2.01 (br, 1H); 13C NMR (100 MHz, CDCl3): d 134.8, 134.7, 133.2,
130.5, 129.9, 129.3, 129.2, 127.5, 127.0, 65.5; MS (EI): m/z 274 (M+,
47), 135 (100).
Experimental
IR spectra were obtained using a Perkin-Elmer 683 instrument.
1H NMR spectra were recorded on a Bruker AC-P400 (400 MHz)
spectrometer with TMS as an internal standard using CDCl3 as the
solvent. 13C NMR (100 MHz) spectra were recorded on a Bruker
AC-P400 (400 MHz) spectrometer using CDCl3 as the solvent.
Mass spectra (EI, 70 eV) were determined on a Finnigan 8230 mass
spectrometer. Microanalyses were obtained using a Perkin-Elmer 240
elemental analyser. Benzene and toluene were freshly distilled from
sodium before use; other reagents were used as received without
further purification.
(Z)-2,3-Bis[(4-methylphenyl)thio]prop-2-en-1-ol (3d): Oil. IR
(neat): n (cm-1) 3391, 3020, 1714, 1564, 1491, 1091, 1017, 805;
1H NMR (400 MHz, CDCl3): d 7.34–7.28 (m, 4H), 7.14–7.09 (m,
4H), 6.89 (s, 1H), 4.09 (s, 2H), 2.33 (s, 3H), 2.30 (s, 3H), 1.98 (br,
1H); 13C NMR (100 MHz, CDCl3): d 137.6, 137.3, 134.3, 131.4,
130.8, 130.6, 130.1, 130.0, 129.4, 65.4, 21.1; MS (EI): m/z 302 (M+,
98), 91 (100); Anal. Calcd for C17H18OS2: C, 67.51; H, 6.00. Found:
C, 67.33; H, 6.05%.
(Z)-1,2-Bis[(4-methylphenyl)thio]-3-methoxyprop-1-ene (3e): Oil.
IR (neat): n (cm-1) 3021, 1714, 1564, 1491, 1119, 1091, 1017, 806;
1H NMR (400 MHz, CDCl3): d 7.36–7.30 (m, 4H), 7.16–7.10 (m,
4H), 6.86 (s, 1H), 3.90 (s, 2H), 3.27 (s, 3H), 2.34 (s, 3H), 2.33 (s,
3H); 13C NMR (100 MHz, CDCl3): d 137.5, 137.1, 134.1, 131.6,
130.8, 130.7, 129.9, 129.8, 129.6, 127.3, 74.4, 58.0, 21.1; MS (EI):
m/z 316 (M+, 59), 161 (100); Anal. Calcd for C18H20OS2: C, 68.31;
H, 6.37. Found: C, 68.38; H, 6.29%.
General procedure for the addition of diaryl disulfides to terminal
alkynes
The Ar2S2 (1.0 mmol), the terminal alkyne (1.5 mmol) and 3 mL
of degassed toluene were combined with the MCM-41-2P-Pd(0)
(40 mg, 0.02 mmol) underAr and the mixture was stirred at 140°C for
2 h in a sealed tube. After cooling to room temperature, the mixture
was filtered and the catalyst was washed with degassed toluene
Table 1 Addition of Ar2S2 to various acetylenes catalysed by MCM-41-2P-Pd(0)a
Entry
R
Ar
Product
Yield b/%
1
2
n-C4H9
n-C4H9
HOCH2
HOCH2
CH3OCH2
Ph
n-C6H13
H2NCH2
n-C6H13
Me3Si
Ph
4-CH3C6H4
Ph
3a
3b
3c
3d
3e
3f
3g
3h
3i
90
91
88
85
87
89
92
86
93
90
89
3
4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
Ph
5
6
7
8
9
Ph
10
11
Ph
3j
3k
HOCH2CH2
Ph
aReactions were conducted under the conditions of 1.5 mmol of acetylene 1 and 1.0 mmol of Ar2S2 2 in the presence of MCM-41-
2P-Pd(0) (2 mol%) in toluene (3 mL) at 140°C for 2 h.
bIsolated yield based on the Ar2S2 2 used.

618 JOURNAL OF CHEMICAL RESEARCH 2009
(Z)-1,2-Bis[(4-methylphenyl)thio]styrene (3f): Oil. IR (neat):
n (cm-1) 3020, 1714, 1539, 1490, 1091, 1017, 803; 1H NMR (400 MHz,
CDCl3): d 7.54–6.97 (m, 14H), 2.35 (s, 3H), 2.23 (s, 3H); 13C NMR
(100 MHz, CDCl3): d 138.9, 137.7, 136.8, 135.8, 131.8, 131.1, 131.0,
130.0, 129.6, 129.2, 128.6, 128.3, 127.4, 126.8, 21.1, 21.0; MS (EI):
m/z 348 (M+, 47), 123 (100); Anal. Calcd for C22H20S2: C, 75.82; H,
5.78. Found: C, 75.57; H, 5.63%.
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2955, 2927, 1582, 1478, 1439, 1092, 1024, 740, 690; 1H NMR (400
MHz, CDCl3): d 7.42–7.19 (m, 10H), 6.56 (s, 1H), 2.24 (t, J = 7.4 Hz,
2H), 1.51–1.45 (m, 2H), 1.26–1.21 (m, 6H), 0.85 (t, J = 7.2 Hz, 3H);
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128.7, 128.4, 127.5, 125.7, –1.2; MS (EI): m/z 316 (M+, 100).
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3353, 3055, 2931, 1582, 1478, 1439, 1024, 742; 1H NMR (400 MHz,
CDCl3): d 7.46–7.20 (m, 10H), 6.73 (s, 1H), 3.71 (t, J = 6.4 Hz, 2H),
2.50 (t, J = 6.4 Hz, 2H), 1.69 (br, 1H); 13C NMR (100 MHz, CDCl3):
d 135.3, 133.4, 133.0, 130.4, 130.1, 129.2, 129.1, 129.0, 127.2, 127.0,
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Received 5 July 2009; accepted 3 Setpember 2009
Paper 09/0668 doi: 10.3184/030823409X12526892025829
Published online: 8 October 2009