Microwave-Assisted Pd-Catalyzed Desulfitative C-S Coupling of Arylsulfinate Metal Salts and Alkanethiols

Article abstract of DOI:10.1080/10426507.2014.906425

This paper reports a palladium-catalyzed C-S coupling of arylsulfinate metal salts and alkanethiols via liberation of sulfur dioxide. The use of PdCl₂ as the catalyst in combination with AgNO₃ as the oxidant under microwave irradiation results in the synthetically and biologically important aryl alkyl sulfides. A variety of arylsulfinate metal salts, such as sodium, potassium, lithium, silver, zinc, and copper salts, are tolerated well in this reaction.

Full text of DOI:10.1080/10426507.2014.906425

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Phosphorus, Sulfur, and Silicon and the
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Microwave-Assisted Pd-Catalyzed
Desulfitative C—S Coupling of
Arylsulfinate Metal Salts and Alkanethiols
Junchen Lia, Xiaojing Bia, Hongmei Wanga & Junhua Xiaoa
a State Key Laboratory of NBC Protection for Civilian, Beijing, P. R.
China
Accepted author version posted online: 18 Jun 2014.Published
online: 13 Dec 2014.
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To cite this article: Junchen Li, Xiaojing Bi, Hongmei Wang & Junhua Xiao (2014) Microwave-Assisted
Pd-Catalyzed Desulfitative C—S Coupling of Arylsulfinate Metal Salts and Alkanethiols, Phosphorus,
Sulfur, and Silicon and the Related Elements, 189:12, 1873-1881, DOI: 10.1080/10426507.2014.906425
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Phosphorus, Sulfur, and Silicon, 189:1873–1881, 2014
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.906425
MICROWAVE-ASSISTED PD-CATALYZED DESULFITATIVE
C S COUPLING OF ARYLSULFINATE METAL SALTS
AND ALKANETHIOLS
Junchen Li, Xiaojing Bi, Hongmei Wang, and Junhua Xiao
State Key Laboratory of NBC Protection for Civilian, Beijing, P. R. China
GRAPHICAL ABSTRACT
Ar SO2M
PdCl2 (20 mol%)
M = Na, K, Li, Ag
AgNO3 (2 equiv)
HS R
+
Ar SR
OR
DMF/DMSO (19/1)
MW, 120 °C, 10 min
(Ar-SO2)2M
M = Zn, Cu
14-75% yield
Abstract This paper reports a palladium-catalyzed C-S coupling of arylsulfinate metal salts
and alkanethiols via liberation of sulfur dioxide. The use of PdCl2 as the catalyst in combina-
tion with AgNO3 as the oxidant under microwave irradiation results in the synthetically and
biologically important aryl alkyl sulfides. A variety of arylsulfinate metal salts, such as sodium,
potassium, lithium, silver, zinc, and copper salts, are tolerated well in this reaction.
Keywords Desulfitative coupling; C-S coupling; arylsulfinate metal salts; thiols
INTRODUCTION
Aryl alkyl sulfide moieties represent one of the most important molecules that are
widely used in many pharmaceuticals, such asthloridazine,1 diltiazem,2 nelfinavir,3 and bi-
calutamide.4 Though great achievements have been made in recent years, current synthetic
methodologies of aryl alkyl sulfide are restricted to the Michael addition of α,β-unsaturated
compounds5 or the coupling of halide substrates with thiols/disulfides.6 The narrow scope
of the α,β-unsaturated compounds and the relatively high reactivity of halide substrates
impedes their further application. Therefore, development of environment-benign and in-
expensive alternatives for the synthesis of aryl alkyl sulfides is still a great challenge. Liu
reported a convenient decarboxylative C S coupling using a bimetallic catalytic system
(Scheme 1a).7 However, only electron-deficient aromatic carboxylic acids were employed
in this reaction. Although aromatic boronic acids exhibit good functional group tolerance,
Received 28 January 2014; accepted 17 February 2014.
Address correspondence to Junhua Xiao, State Key Laboratory of NBC Protection for Civilian, Beijing,
102205, P. R. China. E-mail: xiao.junhua@pku.edu.cn
1873

1874
J. LI ET AL.
Scheme 1 Metal-catalyzed methods for the construction of C-S bond.
the alkanethiol scope is restrained (Scheme 1b).8 The C H activation method is undoubt-
edly the most green and direct approach to aryl alkyl sulfides. The drawback is that present
arene substrates require a directing group or electron-rich substituents (Scheme 1c).9
Recently, increasing attention has been attracted to the desulfitative C C couplings
via extrusion of sulfur dioxide from sulfinate metal salts, RSO2Na10 or (RSO2)2Zn.11
In analogy to decarboxylative couplings that carboxylates could be employed as sources
of carbon nucleophiles and electrophiles,12 we anticipated that arylsulfinate metal salts
might have a similar potential. Besides present desulfitative carbon–carbon coupling meth-
ods, we would like to use arylsulfinate metal salts as a potential carbon electrophile to
react with nucleophiles to construct carbon–heteroatom bond. Langler and co-workers
reported that p-nitrobenzenesulfonates could undergo desulfinative C S coupling with
p-methylbenzenethiol in the presence of sodium hydride to give aryl sulfides through
nucleophilic aromatic substitution.13 Inspired by this pioneering work and in view of
the significance of aryl alkyl sulfides, we report herein a desulfitative C S coupling
using PdCl2 as a catalyst and alkanethiols as nucleophiles under microwave irradiation
(Scheme 1d).
RESULTS AND DISCUSSION
Initial investigations focused on the PdCl2-catalyzed desulfitative C S coupling
of sodium p-toluenesulfinate 1a with methyl 3-mercaptopropanoate 2a under microwave
irradiation. Due to the reductive properties of thiols,7 we selected Ag(I) salts as oxidants
which are known to be efficient oxidants in Pd-catalyzed oxidative couplings.14 As shown
in Table 1, we were pleased to find that the desired C S coupling product 3aa was

PD-CATALYZED DESULFITATIVE C S COUPLING
1875
Table 1 Optimization of the reaction between sodium p-toluenesulfinate 1a and 3-mercaptopropanoate 2aa
Entry
Silver salt (equivalent)
Solvent
Power (W)
Yield of 3aa (%)b
3aa: 4: 5: 6: 7 (%)b,c
1
2
3
4
5
6
7
8
9
10
11
12f
13f
14
15g
Ag2CO3 (2)
Ag2CO3 (2)
Ag2CO3 (2)
Ag2CO3 (2)
Ag2CO3 (2)
Ag2CO3 (2)
Ag2O (2)
AgOAc (2)
Ag2MoO4 (2)
AgNO3 (2)
—
dioxan
toluene
THF
DMF
180
180
120
40
40
40
40
40
40
40
40
40
40
40
40
68
∼0
76
34
46
25
53
50
58
95 (75)e
8
3
0
37
88
83: 6: 1: 5: 5
—
83: 2: 3: 6: 6
56: 5: 37: 0: 2
69: 1: 23: 2: 5
45: 1: 52: 0 : 1
74: 9: 15: 2: 0
70: 7: 13: 2: 8
79: 4: 4: 11: 2
98: 0: 0: 0: 2
14: 36: 0: 10: 40
6: 12: 2: 74: 6
0: 0: 0: 4: 96
45: 9: 1: 7: 38
92: 0: 0 2: 6
DMSO
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
DMF/DMSOd
AgNO3 (2)
—
AgNO3 (1)
AgNO3 (2)
aReaction conditions: 1a (0.36 mmol), 2a (0.3 mmol), PdCl2 (20 mol%), silver salt, solvent (2 mL), MW
irradiation at 120 ◦C for 10 min.
bYields were determined by GC-MS.
cRatio of these peaks was determined by the area normalization method.
d DMF/DMSO = 19/1 (v/v).
e Isolated yield in parenthesis.
f In the absence of PdCl2.
g10 mol% of PdCl2 was used.
formed in 68% yield at 120◦C with 20 mol% PdCl2 and two equivalents of Ag2CO3 in
dioxan (Table 1, entry 1). At the same time, the desulfitative protonation product 4, the
desulfitative homocoupling product 5,10i,10j the reduction/desulfitative coupling product 6,
and the homocoupling product of 2a were generated. The reaction was almost interrupted
when toluene was used as the solvent (Table 1, entry 2). Moderate to good yields could be
obtained when THF, DMF, and DMSO were used as the solvent (Table 1, entries 3–5). By
employing Myers’s solvent system,15 a lower yield of 25% was gained (Table 1, entry 6).
But the side-product distribution was simpler. Further optimization experiments of silver
salts showed that AgNO3 was the ideal oxidant in this catalytic system (Table 1, entries
7–10). When the reaction was carried out in the absence of PdCl2 or AgNO3, only a
small amount of the desired product was generated (Table 1, entries 11–12), whereas the
protonation product 4 and the reduction/desulfitative coupling product 6 were produced. No
desulfitative products (3aa, 4, 5, and 6) were obtained when both PdCl2 and AgNO3 were
not present (Table 1, entry 13), suggesting that PdCl2 and AgNO3 might play a synergetic

1876
J. LI ET AL.
Table 2 Desulfitative C S coupling of 2a with various sodium arylsulfinatesa,b
Entry
1
Sodium arylsulfinate
Product
Yield
75
1a
3aa
2
3
1b
1c
3ba
3ca
52
44
4
5
1d
1e
3da
3ea
50
25
6
1f
3fa
60
aReaction conditions: 1 (0.36 mmol), 2a (0.3 mmol), PdCl2 (20 mol%), AgNO3 (2 equiv), DMF/DMSO
(v/v = 19/1, 2 mL), MW irradiation at 120 ◦C for 10 min.
bIsolated yield.
role in the desulfination. Either decreasing the catalyst loading or the amount of oxidant
resulted in lower yields (Table 1, entries 14–15).
With the optimized reaction conditions in hand, we examined the scope of the
sodium arylsulfinate (Table 2). Electron-donating and electron-withdrawing substituents
on the arylsulfinate were well tolerated in this coupling (Table 2, entries 1–6). In ad-
dition, halide and nitro groups were compatible with the reaction conditions (Table 2,
entries 3–5). The good tolerance of the bromo substituent provided further elaborations in
synthesis.
This desulfitative C S coupling was also effective for other arylsulfinate metal salts,
including K, Li, Ag, Zn, and Cu (Table 3, entries 1–5). The arylsulfinate zinc salt showed
high reactivity to give the coupling product in 62% yield (Table 3, entry 4).
We then explored the use of other alkanethiols in these transformations. As depicted
in Table 4, the desulfitative C S coupling proceeded well with electron-deficient thiols
(2b and 2c) and relatively sterically hindered thiol (2d).
Based on the above observations and previous work,10,12 the arylsulfinate metal salts
should cause desulfination directly in the presence of the Pd/Ag catalytic system to give an
aryl-metal intermediate which then undergoes further transformations. This type of reaction
is disparate from the arylsulfonates-based desulfitative C S coupling which proceeds via
a nucleophilic aromatic substitution mechanism.13

PD-CATALYZED DESULFITATIVE C S COUPLING
1877
Table 3 Desulfitative C S coupling of 2a with other arylsulfinate metal saltsa,b
Entry
1
Arylsulfinate metal salt
Product
Yield
33
1g
1h
1i
3ga
3ha
3ia
2
3
4
5
54
42
62
14
1j
3ja
3ka
1k
aReaction conditions: 1 (0.36 mmol or 0.18 mmol), 2a (0.3 mmol), PdCl2 (20 mol%), AgNO3 (2 equiv),
DMF/DMSO (v/v = 19/1, 2 mL), MW irradiation at 120 ◦C for 10 min.
bIsolated yield.
Table 4 Desulfitative C S coupling of 1a with other alkanethiolsa,b
Entry
1
Alkanethiol
Product
Yield
48
2b
2c
2d
3ab
3ac
3ad
2
3
38
63
aReaction conditions: 1a (0.36 mmol or 0.18 mmol), 2 (0.3 mmol), PdCl2 (20 mol%), AgNO3 (2 equiv),
DMF/DMSO (v/v = 19/1, 2 mL), MW irradiation at 120 ◦C for 10 min.
bIsolated yield.

1878
J. LI ET AL.
CONCLUSION
We have developed a Pd-catalyzed desulfitative C S coupling for the synthesis of
aryl alkyl sulfides under microwave irradiation. The reaction is shown to be amenable to
halide and nitro substituents on the arylsulfinate metal salts. Further efforts are focused on
expanding the substrate scope and understanding the mechanism of the transformation.
EXPERIMENTAL
All commercially obtained reagents for the desulfitative C S coupling reaction were
used as received; sodium arylsulfinates and potassium arylsulfinates were prepared ac-
cording to the literature;16 silver arylsulfinates were prepared according to the literature.17
Dichloromethane, hexane, and ethyl acetate (EA) were distilled prior to use. All reactions
were carried out in the air. Reactions were monitored by thin layer chromatography (TLC)
carried out on 0.25 mm E. Merck silica gel plates (60F-254) using UV light as the visual-
izing agent. Qingdao haiyang silica gel (200–300 mesh) was used for flash column chro-
matography. NMR spectra of CDCl3 solutions were recorded on Bruker Advance III-400
instruments at 400 MHz (1H) or 100 MHz (13C) and calibrated using residual undeuterated
1
solvent as an internal reference (TMS @ 0.00 ppm H NMR, CHCl3 @ 77.16 ppm 13C
NMR). The following abbreviations (or combinations thereof) were used: s = singlet, d =
doublet, t = triplet, q = quartet, m = multiplet. Mass spectra were recorded on Polaris Q
using an electron impact ion source (70 eV).
The reactions involving microwave irradiation were conducted under air in heavy
walled glass vessels purchased from CEM. The microwave heating was performed in a
CEM DISCOVER SCLASS autofocus coupling single-mode microwave cavity using a
dynamic method. The reaction mixtures were stirred with a magnetic stir bar at high speed
during the irradiation. The temperature, pressure, and irradiation power were monitored
during the course of the reactions using the provided software.
General Procedure for the Preparation of Aryl Alkyl Sulfides
Arylsulfinate metal salt (0.36 mmol or 0.18 mmol), PdCl2 (0.06 mmol), AgNO3
(0.6 mmol), DMF/DMSO (v/v = 19/1, 2 mL), and thiol (0.3 mmol) were added to the
microwave tube. The tube was sealed and stirred for 5 min at ambient temperature. The tube
was then heated at 40 W for 10 min at 120◦C. After cooling down, the resulting suspensions
were filtered off and washed with CH2Cl2. A small amount of silica gel was added into the
filtrate, and then evaporated. The residue was purified by flash chromatography on silica
with hexane/EA to provide the desired product.
Methyl 3-(p-tolylthio)propanoate (3aa)
1
Oil, Rf = 0.44 (Vhexane/VEA = 4/1). H NMR: δ 7.28 (d, 2H, ArH, J = 8.0 Hz),
7.10 (d, 2H, ArH, J = 8.0 Hz), 3.66 (s, 3H, OCH3), 3.11 (t, 2H, SCH2, J = 7.4 Hz), 2.59
(t, 2H, COCH2, J = 7.4 Hz), 2.31 (s, 3H, ArCH3). 13C NMR: δ 172.2, 136.9, 131.4, δ131.1
(2 × C), 129.3(2 × C), 51.8, 34.36, 29.83, 21.05. MS: m/z (%): 210 (M+, 100), 179 (10),
150 (42), 135 (35).

PD-CATALYZED DESULFITATIVE C S COUPLING
1879
Methyl 3-(phenylthio)propanoate (3ba)
Oil, Rf = 0.46 (Vhexane/VEA = 4/1). 1H NMR: δ 7.36 (d, 2H, ArH, J = 7.2 Hz), 7.29
(t, 2H, ArH, J = 7.5 Hz), 7.20 (t, 1H, ArH, J = 7.5 Hz), 3.67 (s, 3H, OCH3), 3.16 (t, 2H,
SCH2, J = 7.4 Hz), 2.63 (t, 2H, COCH2, J = 7.4 Hz). 13C NMR: δ 172.2, 136.3, 130.2
(2 × C), 129.1 (2 × C), 126.6, 51.8,34.3, 29.1. MS: m/z (%): 196 (M+, 100), 165 (8), 136
(62).
Methyl 3-(4-chlorophenylthio)propanoate (3ca)
Oil, Rf = 0.47 (Vhexane/VEA = 4/1). 1H NMR: δ 7.28 (dd, 4H, ArH, J = 7.8 Hz, J =
7.8 Hz), 3.68 (s, 3H, OCH3), 3.14 (t, 2H, SCH2, J = 7.3 Hz), 2.62 (t, 2H, COCH2, J =
7.3 Hz). 13C NMR: δ 172.1, 133.9, 132.8, 131.6 (2 × C), 129.3 (2 × C), 52.00, 34.2, 29.5.
MS: m/z (%): 230 (M+−1, 84), 199 (11), 170 (62), 157 (21), 143 (14), 135 (46).
Methyl 3-(4-bromophenylthio)propanoate (3da)
Oil, Rf = 0.43 (Vhexane/VEA = 4/1). 1H NMR: δ 7.41 (d, 2H, ArH, J = 8.4 Hz), 7.23
(d, 2H, ArH, J = 8.4 Hz), 3.68 (s, 3H, OCH3), 3.15 (t, 2H, SCH2, J = 7.3 Hz), 2.62 (t,
2H, COCH2, J = 7.3 Hz). 13C NMR: δ 172.1, 134.6, 132.2 (2 × C), 131.7 (2 × C), 120.7,
52.0, 34.2, 29.3. MS: m/z (%): 276 (M++1, 100), 274 (M+−1, 96), 245 (8), 216 (70), 203
(24), 189 (16), 135 (71).
Methyl 3-(4-nitrophenylthio)propanoate (3ea)
Oil, Rf = 0.26 (Vhexane/VEA = 4/1). 1HNMR:δ 8.14 (d, 2H, ArH, J = 8.8 Hz), 7.36
(d, 2H, ArH, J = 8.8 Hz), 3.72 (s, 3H, OCH3), 3.32 (t, 2H, SCH2, J = 7.3 Hz), 2.71 (t, 2H,
COCH2, J = 7.3 Hz).13C NMR: δ 171.7, 146.4, 145.6, 126.9 (2 × C), 124.2 (2 × C), 52.2,
33.6, 27.8. MS: m/z (%): 241 (M+, 84), 224 (42), 209 (53), 192 (18), 181 (100), 164 (31),
134 (50).
Methyl 3-(4-tert-butylphenylthio)propanoate (3fa)
Oil, Rf = 0.46 (Vhexane/VEA = 4/1). 1HNMR: δ 7.32 (b, 4H, ArH), 3.67 (s, 3H, OCH3),
3.13 (t, 2H, SCH2, J = 7.4 Hz), 2.62 (t, 2H, COCH2, J = 7.4 Hz), 1.30 (s, 9H, C(CH3)3).
13C NMR: δ 172.4, 150.2, 131.6, 130.7 (2 × C), 126.2 (2 × C), 51.9, 34.6, 31.4 (3 × C),
31.1, 29.7. MS: m/z (%): 252 (M+, 47), 237 (100), 205 (19), 177 (18), 163 (28), 149 (18),
135 (10).
Methyl 2-(p-tolylthio)acetate (3ab)
Oil, Rf = 0.46 (Vhexane/VEA = 4/1). 1H NMR: δ 7.39 (t, 2H, ArH, J = 8.5 Hz), 7.01
(t, 2H, ArH, J = 8.5 Hz), 3.68 (s, 3H, OCH3), 3.11 (t, 2H, SCH2, J = 7.3 Hz), 2.59 (t, 2H,
COCH2, J = 7.3 Hz), 2.04 (s, 3H, ArCH3). 13C NMR: δ 172.2, 133.6 (2 × C), 133.5 (2 ×
C), 130.1, 129.7, 51.9, 34.4, 21.2. MS: m/z (%): 196 (M+, 100), 137 (54).
Ethyl 2-(p-tolylthio)acetate (3ac)
Oil, Rf = 0.49 (Vhexane/VEA = 4/1). 1H NMR: δ 7.33 (d, 2H, ArH, J = 8.0 Hz), 7.11
(d, 2H, ArH, J = 8.0 Hz), 4.15 (q, 2H, OCH2, J = 7.1 Hz), 3.57 (s, 2H, SCH2), 2.32
(s, 3H, ArCH3), 1.22 (t, 3H, OCH2CH3, J = 7.1 Hz). 13C NMR: δ 169.9, 137.4, 131.3,

1880
J. LI ET AL.
131.1 (2 × C), 129.9 (2 × C), 61.5, 37.6, 21.2, 14.2. MS: m/z (%): 210 (M+, 100), 182 (5),
137 (60).
Ethyl 2-(p-tolylthio)propanoate (3ad)
Oil, Rf = 0.57 (Vhexane/VEA = 4/1). 1H NMR: δ 7.36 (d, 2H, ArH, J = 8.0 Hz), 7.11
(d, 2H, ArH, J = 8.0 Hz), 4.11 (q, 2H, OCH2, J = 7.0 Hz), 3.70 (q, 1H, SCH, J = 7.1 Hz),
2.33 (s, 3H, ArCH3), 1.45 (d, 3H, SCHCH3, J = 7.1 Hz), 1.19 (t, 3H, OCH2CH3, J =
7.1 Hz). 13C NMR: δ 172.8, 138.5, 133.9 (2 × C), 129.8 (2 × C), 129.5, 61.2, 45.7, 21.3,
17.5, 14.2. MS: m/z (%): 224 (M+, 75), 151 (100).
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