Copper-catalyzed selective single arylsulfanylation of aryl diiodides with aryl thiols

Article abstract of DOI:10.1055/s-0033-1338525

Selective single arylsulfanylation reactions of aryl diiodides with aryl or hetaryl thiols to give a broad array of iodine-functionalized sulfides were developed. Further elaboration of the iodine-containing products to provide a variety of aryl and hetaryl sulfides through coupling reactions was also demonstrated. Georg Thieme Verlag Stuttgart, New York.

Full text of DOI:10.1055/s-0033-1338525

PAPER
▌2977
paper
Copper-Catalyzed Selective Single Arylsulfanylation of Aryl Diiodides with
Aryl Thiols
Selective Single Arylsulfanylation of Aryl Diiodides
Yunyun Liu,a Hang Wang,a Xiaoji Cao,b Zheng Fang,a Jie-Ping Wan*a
a
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. of China
b
Research Centre of Analysis and Measurement, Zhejiang University of Technology, 18 Chaowang Road, Hangzhou, Zhejiang 310014,
P. R. of China
Fax +86(791)88120380; E-mail: wanjieping@jxnu.edu.cn
Received: 03.07.2013; Accepted after revision: 12.08.2013
sulfides relies on the addition reaction of arylmagnesium
Abstract: Selective single arylsulfanylation reactions of aryl diio-
compounds with arynes.14
dides with aryl or hetaryl thiols to give a broad array of iodine-func-
tionalized sulfides were developed. Further elaboration of the
iodine-containing products to provide a variety of aryl and hetaryl
sulfides through coupling reactions was also demonstrated.
In the context of the versatile reactivity of the iodoaryl
backbone for the synthesis of various elaborated aryl
products, a straightforward approach to selective single
C–S coupling reactions of diiodoaryls would be highly de-
sirable, as this would provide iodoaryl sulfides, useful as
precursors of more-complex sulfur-containing products.
As a continuation of our longstanding research efforts in
copper-catalyzed coupling chemistry,4,8b,15 we wish to re-
port a simple and efficient method for the synthesis of io-
doaryl-functionalized sulfides through copper-catalyzed
selective single Ullmann C–S coupling reactions of thio-
phenols with diiodoaryl compounds.
Key words: copper, cross-coupling, iodides, sulfides, catalysis
The copper-catalyzed Ullmann coupling reaction, which
includes carbon–carbon and carbon–heteroatom coupling
reactions, is now regarded as the basic and most powerful
tool for constructing sp2 C–C, C–N, C–O, and C–S bonds
in organic synthesis.1 As a result of the revolutionary dis-
covery of ligand-assisted Ullmann reactions, researches
on these reactions have achieved breathtaking progress,
and in the last two decades the reactions have permeated
almost to every corner of synthetic organic chemistry,2 in-
cluding syntheses of natural products,3 biologically active
organic compounds,3 structurally diverse small heterocy-
clic molecules,4 polymers, and many industrial chemical
intermediates. In documented versions of the Ullmann
coupling reaction, C–S coupling of S-nucleophiles, such
as thiophenols or thiols, to aryl or vinyl halides is the ma-
jor strategy for the synthesis of aryl and vinyl thioethers5
and, by further tandem reactions, for the synthesis of var-
ious sulfur-containing heterocycles.6 During the last de-
cade, considerable efforts have been made to develop
improved protocols for C–S coupling reactions to provide
easier access to these sulfur-containing products. The
main tactics involve identifying alternative metal cata-
lysts,7 the development of new ligands,8 the use of cleaner
reaction media9 or transition-metal-free catalytic sys-
tems,10 and the application of new sources of sulfur.11 In
most reported catalytic C–S coupling reactions of diiodo-
benzenes, the corresponding double-thiolated sulfides are
the major or sole products.7d,12 Mao and co-workers have
systematically investigated the selective double C–S cou-
pling reactions of diiodobenzenes with phenols and thio-
phenols in the presence of iron and copper cocatalysts.13
Interestingly, however, there are few examples of selec-
tive single C–S coupling reactions of diiodobenzenes with
S-nucleophiles. A known route to iodine-functionalized
We focused initially on the model reaction of 1,2-diiodo-
benzene (1a) with benzenethiol (2a). On the basis of our
previous experiences with enaminone ligand-assisted
coupling reactions, we first performed the reaction by us-
ing the enaminone ligand L1 in the presence of copper(I)
iodide in dimethyl sulfoxide at 100 °C for 12 hours, and
we obtained the monothiolated product 3a as the major
product together with the dithiolated product 4a in a 62:11
ratio (Table 1, entry 1). The selectivity of this reaction en-
couraged us to attempt to optimize the reaction conditions
for greater selectivity. First, we screened various enami-
none ligands L1–4 and the classical ligand 1,10-phenan-
throline (L5), but we found no improvement (entries 2–5).
Furthermore, changing the copper species to copper(II)
acetate, copper(I) bromide, copper(II) bromide, or cop-
per(II) oxide also failed to give better results (entries 6–9).
Changing the reaction medium and the base additive also
failed to enhance the yield or the selectivity of the reaction
(entries 10–15). Lowering the reaction temperature led to
poor conversion (entry 16), whereas higher temperatures
resulted in much lower selectivity (entry 17). However,
prolonging the reaction time to 18 hours proved to be ef-
fective in providing product 3a in better yield and greater
selectivity (entry 18), although increasing the reaction
time further to 21 hours produced no additional improve-
ment (entry 19).
Having identified conditions that permitted highly selec-
tive single thiolation of 1,2-diiodobenzene, we went on to
examine the reactions of 1,2-, 1,3-, and 1,4-diiodobenzene
(1a–c, respectively) with various thiophenols 2 to demon-
strate the general applicability of our approach (Scheme 1).
SYNTHESIS 2013, 45, 2977–2982
Advanced online publication: 02.09.2013
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DOI: 10.1055/s-0033-1338525; Art ID: SS-2013-H0453-OP
© Georg Thieme Verlag Stuttgart · New York

2978
Y. Liu et al.
PAPER
selectivities and yields. Although dithiolated byproducts
of type 4 were also obtained, their yields were not calcu-
lated as they were found in rather small amounts and, in
most cases, were difficult to isolate by thin-layer chroma-
tography or column chromatography. Particularly good
results were obtained with 1,3-benzothiazole-2-thiol (en-
tries 10 and 18). Arylation of alkylbenzenethiols gave the
corresponding sulfides in slightly higher yields than those
obtained from halobenzenethiols. However, no significant
differences in product yields was observed among the var-
ious benzenethiols, probably as a result of the formation
of byproducts. All products were characterized by a range
of spectroscopic techniques and the structures of products
3a and 3d were confirmed by single-crystal X-ray crystal-
lographic analysis (Figure 1).16
Table 1 Optimization of Conditions for a Selective Single C–S
Coupling Reaction of 1,2-Diiodobenzene
SH
I
S
Cu (cat.)
S
S
I
I
1a
2a
3a
4a
Entrya Ligand Copper
catalyst
Base
Solvent
Yields of 3a
and 4a (%)b
1
L1
L2
L3
L4
L5
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
CuI
CuI
CuI
CuI
CuI
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
62:11
43:13
32:16
50:12
32:17
35:16
48:12
38:13
33:19
17:7
2
3
4
5
Table 2 Synthesis of Iodophenyl Thioethers by Selective C–S
Coupling of Aryl Diiodides
6
Cu(OAc)2 Cs2CO3
7
CuBr
CuBr2
CuO
CuI
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
SH
S
CuI, L1/Cs2CO3
I
R
R
I
8
DMSO, N2, 100 °C
I
1
2
3
9
Entrya Diiodobenzene Thiol
Product Yield
(%)b
10
11
12
13
14
15
16c
17d
18e
19f
CuI
1,4-dioxane 32:19
1
1,2-I2C6H4 (1a) PhSH
3a
3b
3c
3d
3e
3f
79
83
81
69
81
76
80
74
81
93
80
86
85
71
78
83
72
90
86
85
83
CuI
toluene
50:26
43:19
48:11
37:17
48:23
18:6
2
1a
1a
1a
1a
1a
1a
1a
1a
1a
4-TolSH
CuI
t-BuOK DMSO
Et3N DMSO
Na2CO3 DMSO
3
4-i-PrC6H4SH
4-FC6H4SH
4-ClC6H4SH
4-BrC6H4SH
3-TolSH
CuI
4
CuI
5
CuI
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DMSO
DMSO
DMSO
DMSO
6
CuI
7
3g
3h
3i
CuI
79:7
8
2-H2NC6H4SH
L1
CuI
76:9
9
naphthalene-2-thiol
O
Me
N
O
10
11
12
13
14
15
16
17
18
20
21
22
1,3-benzothiazole-2-thiol 3j
O
NHPh
Me
Me
N
R
OH
1,3-I2C6H4 (1b) PhSH
3k
3l
Me
O2N
N
N
1b
1b
1b
1b
1b
1b
1b
4-TolSH
L4
L5
L1 R = H
L2 R = OMe
L3
4-i-PrC6H4SH
4-FC6H4SH
3m
3n
3o
3p
3q
a General conditions: 1a (0.2 mmol), 2a (0.3 mmol), Cu catalyst (0.04
mmol), ligand (0.04 mmol), base (0.4 mmol), DMSO (1 mL), 100 °C,
12 h, under N2.
4-BrC6H4SH
3-TolSH
b Yield of isolated product, based on 1a.
c At 110 °C.
d At 90 °C.
naphthalene-2-thiol
d Reaction time 18 h
e Reaction time 21 h.
1,3-benzothiazole-2-thiol 3r
1,4-I2C6H4 (1c) PhSH
3s
3t
To our delight, the expected reaction occurred with all
three diiodobenzenes, and some typical results are listed
in Table 2. In general, thiophenols containing various
functional groups, such as alkyl, halo, or amino groups,
and hetaryl thiols such as 1,3-benzothiazole-2-thiol react-
ed with diiodobenzenes to give the corresponding mono-
thiolated iodobenzenes with good to excellent
1c
1c
4-TolSH
4-ClC6H4SH
3u
a General conditions: 1 (0.2 mmol), 2 (0.3 mmol), CuI (0.04 mmol),
L1 (0.04 mmol), Cs2CO3 (0.4 mmol), DMSO (1 mL), 100 °C, 18 h,
under N2.
b Yield of isolated product, based on 1.
Synthesis 2013, 45, 2977–2982
© Georg Thieme Verlag Stuttgart · New York

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Selective Single Arylsulfanylation of Aryl Diiodides
2979
All chemicals were obtained from commercial sources and used as
1
received. Reactions were monitored by TLC. H and 13C NMR
spectra were recorded on a Bruker Avance 400 spectrometer with
CDCl3 as solvent. The reported chemical shifts are relative to TMS
as internal standard. Melting points of all solid products were deter-
mined in X-4 apparatus and are uncorrected. HRMS data were re-
corded in the EI or ESI mode on a micrOTOF-QII QTOF mass
spectrometer (Bruker).
(Het)aryl Sulfides 3; General Procedure
Diiodobenzene 1 (0.2 mmol), (het)aryl thiol 2 (0.3 mmol), CuI (0.04
mmol), ligand L1 (0.04 mmol), and Cs2CO3 (0.4 mmol) were added
to DMSO (1 mL) in a 25-mL round-bottomed flask equipped with
a stirring bar. The mixture was stirred at 100 °C for 18 h under N2
then cooled to r.t. H2O (8 mL) was added and the resulting residue
was extracted with EtOAc (3 × 8 mL). The organic layers were
combined, dried (MgSO4), and concentrated under reduced pres-
sure. The residue was purified by silica flash column chromatogra-
phy (petroleum ether).
2-Iodophenyl Phenyl Sulfide (3a)14
White solid; yield: 49 mg (79%); mp 55–57 °C (Lit.14 55.6–
56.0 °C).
IR (KBr): 1564, 1469, 1007, 749, 533 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.83 (d, J = 8.0 Hz, 1 H), 7.44–
7.34 (m, 5 H), 7.19 (t, J = 7.6 Hz, 1 H), 6.93 (d, J = 8.0 Hz, 1 H),
6.87 (t, J = 7.6 Hz, 1 H).
Figure 1 ORTEP drawings of (a) 3a and (b) 3d16
13C NMR (100 MHz, CDCl3): δ = 142.29, 139.68, 133.89, 133.16,
129.69, 129.43, 128.78, 128.39, 127.49, 99.34.
Having establishing a method for the synthesis of the io-
do(het)aryl sulfides 3, we then attempted to use the prod-
ucts for the synthesis of more-elaborated sulfides by
various coupling reactions of the residual aryl C–I bond.
Iodophenyl sulfides 3a and 3k were subjected to a typical
Suzuki–Miyaura reaction17 and an Ullmann C–N coupling
reaction, respectively (Scheme 1). The corresponding
coupled products 5 and 7, respectively, were obtained in
excellent yields.
2-Iodophenyl 4-Tolyl Sulfide (3b)
Yellow solid; yield: 54 mg (83%); mp 69–71 °C.
IR (KBr): 2918, 1510, 1450, 1003, 735, 522 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 8.0 Hz, 1 H), 7.38 (d,
J = 7.2 Hz, 2 H), 7.22 (d, J = 7.6 Hz, 2 H), 7.15 (t, J = 7.6 Hz, 1 H),
6.81 (q, J = 8.8 Hz, 2 H), 2.38 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 143.33, 139.49, 138.99, 134.10,
130.55, 129.76, 128.61, 128.24, 126.89, 97.82, 21.30.
HRMS (ESI): m/z [M + H]+ calcd for C13H12IS: 326.9704; found:
326.9694.
B(OH)2
I
S
S
Pd(OAc)2, K2CO3
2-Iodophenyl 4-Isopropylphenyl Sulfide (3c)
Yellow oily mass; yield: 57 mg (81%).
ethyl lactate–H2O, 60 °C
91%
IR (KBr): 2959, 2868, 1439, 1008, 744, 556 cm–1.
3a
S
OMe
5
OMe
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 7.6 Hz, 1 H), 7.38 (d,
J = 8.0 Hz, 2 H), 7.24 (d, J = 7.6 Hz, 2 H), 7.15 (t, J = 7.6 Hz, 1 H),
6.87–6.80 (m, 2 H), 2.94–2.89 (m, 1 H), 1.26 (d, J = 7.2 Hz, 6 H).
4
S
N
CuI, L1, Cs2CO3
DMF, 120 °C
81%
N
H
13C NMR (100 MHz, CDCl3): δ = 149.84, 143.31, 139.47, 134.13,
129.97, 128.64, 128.25, 127.95, 126.89, 97.80, 33.92, 23.89.
HRMS (ESI): m/z [M + H]+ calcd for C15H16IS: 355.0017; found:
3k
N
I
7
6
N
355.0018.
Scheme 1 Synthesis of elaborated sulfides from iodophenyl sulfides
4-Fluorophenyl 2-Iodophenyl Sulfide (3d)14
White solid; yield: 46 mg (69%); mp 94–96 °C (Lit.14 93.7–94.7
°C).
IR (KBr): 1530, 1454, 1280, 1006, 741, 528 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.0 Hz, 1 H), 7.45–
7.41 (m, 2 H), 7.17 (t, J = 8.0 Hz, 1 H), 7.07 (t, J = 8.4 Hz, 2 H),
6.85 (q, J = 6.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 163.03 (d, JF–C = 248 Hz),
142.71, 139.66, 136.00 (d, JF–C = 8 Hz), 128.78, 128.49, 127.29,
117.09, 116.87, 98.18.
In conclusion, we have developed the first generally ap-
plicable method for effective synthesis of iodoaryl sul-
fides by selective single C–S coupling reactions of
(het)aryl thiols with 1,2-, 1,3-, or 1,4-diiodobenzene in the
presence of a readily available enaminone ligand and cop-
per(I) iodide catalyst to give a broad range of iodine-func-
tionalized sulfides, potentially useful as precursors for
syntheses of various elaborated sulfides.
© Georg Thieme Verlag Stuttgart · New York
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4-Chlorophenyl 2-Iodophenyl Sulfide (3e)14
HRMS (ESI): m/z [M + H]+ calcd for C13H9INS2: 369.9221; found:
369.9220.
White solid; yield: 56 mg (81%); mp 89–91 °C (Lit.14 89–90 °C).
IR (KBr): 1521, 1453, 1005, 768, 739, 536 cm–1.
3-Iodophenyl Phenyl Sulfide (3k)
1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J = 8.0 Hz, 1 H), 7.34 (s,
3 H), 7.26–7.21 (m, 2 H), 6.99 (d, J = 8.0 Hz, 1 H), 6.90 (t, J = 7.6
Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 141.41, 139.88, 134.37, 133.91,
132.78, 130.01, 129.84, 128.92, 127.99, 100.08.
Yellow gummy product; yield: 50 mg (80%).
IR (KBr): 1570, 1496, 1060, 776, 528 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.62 (s, 1 H), 7.52 (d, J = 8.0 Hz,
1 H), 7.38–7.28 (m, 5 H), 7.22 (d, J = 8.0 Hz, 1 H), 6.98 (t, J = 8.0
Hz, 1 H).
4-Bromophenyl 2-Iodophenyl Sulfide (3f)14
13C NMR (100 MHz, CDCl3): δ = 138.95, 138.31, 135.67, 134.15,
132.06, 130.61, 129.50, 129.26, 127.90, 94.81.
HRMS (EI): m/z [M]+ calcd for C12H9IS: 311.9470; found:
311.9461.
White solid; yield: 59 mg (76%); mp 89–90 °C (Lit.14 88.1–88.8
°C).
IR (KBr): 1563, 1468, 1006, 747, 642, 531 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.85 (dd, J1 = 8.0 Hz, J2 = 1.2 Hz,
1 H), 7.50–7.47 (m, 2 H), 7.26–7.21 (m, 3 H), 7.02 (dd, J1 = 8.0 Hz,
J2 = 1.2 Hz, 1 H), 6.91 (td, J1 = 8.0 Hz, J2 = 1.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 141.16, 139.91, 134.00, 133.55,
132.78, 130.25, 128.99, 128.14, 122.39, 100.46.
3-Iodophenyl 4-Tolyl Sulfide (3l)
Yellow gummy product; yield: 56 mg (86%).
IR (KBr): 2920, 1566, 1491, 1057, 770, 521 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.47 (s, 1 H), 7.40 (d, J = 7.2 Hz,
1 H), 7.24 (d, J = 7.6 Hz, 2 H), 7.08 (t, J = 8.0 Hz, 3 H), 6.87 (t,
J = 8.0 Hz, 1 H), 2.28 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 140.21, 138.48, 137.14, 135.05,
133.11, 130.45, 130.35, 129.68, 128.08, 94.74, 21.24.
2-Iodophenyl 3-Tolyl Sulfide (3g)
Yellow gummy product; yield: 52 mg (80%).
IR (KBr): 2920, 1440, 1008, 744, 552 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 7.6 Hz, 1 H), 7.28–
7.24 (m, 3 H), 7.18 (s, 2 H), 6.91–6.85 (m, 2 H), 2.35 (s, 3 H).
HRMS (EI): m/z [M]+ calcd for C13H11IS: 325.9626; found:
325.9637.
13C NMR (100 MHz, CDCl3): δ = 142.63, 139.59, 133.91, 133.43,
130.38, 129.51, 129.34, 129.15, 128.72, 127.26, 98.93, 21.34.
HRMS (ESI): m/z [M + H]+ calcd for C13H12IS: 326.9704; found:
326.9712.
3-Iodophenyl 4-Isopropylphenyl sulfide (3m)
Yellow gummy product; yield: 60 mg (85%).
IR (KBr): 2967, 2872, 1441, 1008, 743, 559 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.59 (s, 1 H), 7.49 (d, J = 8.0 Hz,
1 H), 7.33 (d, J = 8.4 Hz, 2 H), 7.21 (d, J = 8.0 Hz, 2 H), 7.16 (d,
J = 7.6 Hz, 1 H), 6.96 (t, J = 8.0 Hz, 1 H), 2.94–2.89 (m, 1 H), 1.22
(d, J = 6.8 Hz, 6 H).
13C NMR (100 MHz, CDCl3): δ = 149.22, 139.94, 137.47, 135.19,
132.85, 130.49, 130.19, 128.41, 127.73, 94.73, 33.86, 23.91.
2-[(2-Iodophenyl)sulfanyl]aniline (3h)
Brown solid; yield: 48 mg (74%); mp 98–100 °C.
IR (KBr): 3463, 1528, 1456, 1004, 732, 527 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.69 (d, J = 7.6 Hz, 1 H), 7.37 (d,
J = 7.2 Hz, 1 H), 7.22–7.17 (m, 1 H), 7.05 (t, J = 7.6 Hz, 1 H), 6.74–
6.68 (m, 3 H), 6.52 (d, J = 8.0 Hz, 1 H), 3.83 (br s, 2 H).
HRMS (ESI): m/z [M + H]+ calcd for C15H16IS: 355.0017; found:
13C NMR (100 MHz, CDCl3): δ = 148.81, 141.46, 139.40, 137.69,
355.0019.
131.75, 128.65, 126.49, 125.85, 119.13, 115.66, 114.67, 95.76.
HRMS (EI): m/z [M]+ calcd for C12H10INS: 326.9579; found:
4-Fluorophenyl 3-Iodophenyl Sulfide (3n)
Yellow gummy product; yield: 47 mg (71%).
326.9579.
IR (KBr): 1568, 1486, 1280, 1058, 766, 521 cm–1.
2-Iodophenyl 2-Naphthyl Sulfide (3i)
1H NMR (400 MHz, CDCl3): δ = 7.52 (t, J = 8.0 Hz, 2 H), 7.43–
7.39 (m, 2 H), 7.15 (d, J = 8.0 Hz, 1 H), 7.06 (t, J = 8.4 Hz, 2 H),
6.98 (t, J = 8.0 Hz, 1 H).
Yellow solid; yield: 59 mg (81%); mp 59–61 °C.
IR (KBr): 1439, 1009, 748, 525 cm–1.
13C NMR (100 MHz, CDCl3): δ = 164.04, 161.57, 139.64, 137.30,
1H NMR (400 MHz, CDCl3): δ = 7.96 (s, 1 H), 7.85–7.77 (m, 4 H),
7.53–7.48 (m, 2 H), 7.44 (dd, J1 = 8.0 Hz, J2 = 1.6 Hz, 1 H), 7.15 (t,
J = 8.0 Hz, 1 H), 6.93 (d, J = 8.0 Hz, 1 H), 6.86 (t, J = 8.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 142.34, 139.72, 133.97, 132.86,
132.57, 131.21, 130.02, 129.55, 129.41, 128.80, 127.86, 127.76,
127.55, 126.84, 126.78, 99.24.
135.14 (d, JF–C = 7.0 Hz), 130.59, 128.61, 128.22, 116.87 (d, JF–C
=
22.0 Hz), 94.81.
HRMS (EI): m/z [M]+ calcd for C12H8FIS: 329.9375; found:
329.9389.
4-Bromophenyl 3-Iodophenyl Sulfide (3o)
Yellow solid; yield: 61 mg (78%); mp 62–64 °C.
HRMS (ESI): m/z [M + H]+ calcd for C16H12IS: 362.9704; found:
362.9697.
IR (KBr): 1565, 1486, 1055, 759, 657, 519 cm–1.
2-[(2-Iodophenyl)sulfanyl]-1,3-benzothiazole (3j)
1H NMR (400 MHz, CDCl3): δ = 7.56 (s, 1 H), 7.48 (d, J = 8.0 Hz,
1 H), 7.36 (d, J = 8.0 Hz, 2 H), 7.17–7.12 (m, 3 H), 6.93 (t, J = 8.0
Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 138.81, 137.90, 136.19, 133.83,
133.10, 132.55, 130.79, 129.77, 121.88, 94.95.
HRMS (EI): m/z [M]+ calcd for C12H8BrIS: 389.8575; found:
389.8582.
Yellow gummy product; yield: 74 mg (93%).
IR (KBr): 1556, 1459, 1441, 1003, 753, 523 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.96 (dd, J1 = 8.0 Hz, J2 = 1.2 Hz,
1 H), 7.84 (d, J = 8.0 Hz, 1 H), 7.77 (dd, J1 = 8.0 Hz, J2 = 1.6 Hz, 1
H), 7.61 (d, J = 7.6 Hz, 1 H), 7.40–7.33 (m, 2 H), 7.24–7.18 (m, 1
H), 7.12–7.08 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 167.73, 153.91, 140.87, 136.32,
135.78, 135.74, 131.66, 129.70, 126.27, 124.57, 122.19, 120.95,
107.56.
3-Iodophenyl 3-Tolyl Sulfide (3p)
Yellow gummy product; yield: 54 mg (83%).
Synthesis 2013, 45, 2977–2982
© Georg Thieme Verlag Stuttgart · New York

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Selective Single Arylsulfanylation of Aryl Diiodides
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IR (KBr): 2919, 1569, 1493, 1057, 767, 522 cm–1.
HRMS (EI): m/z [M]+ calcd for C12H8ClIS: 345.9080; found:
345.9068.
1H NMR (400 MHz, CDCl3): δ = 7.61 (s, 1 H), 7.52 (d, J = 8.0 Hz,
1 H), 7.23–7.19 (m, 4 H), 7.11 (d, J = 7.2 Hz, 1 H), 6.98 (t, J = 8.0
Hz, 1 H), 2.33 (s, 3 H)
13C NMR (100 MHz, CDCl3): δ = 138.89, 138.78, 137.55, 134.97,
133.11, 132.34, 130.05, 128.83, 128.52, 128.36, 94.27, 20.86.
HRMS (EI): m/z [M]+ calcd for C13H11IS: 325.9626; found:
325.9631.
4′-Methoxy-2-(phenylsulfanyl)biphenyl (5)
The reaction of 1,2-diiodobenzene (3a; 0.5 mmol) and (4-methoxy-
phenyl)boronic acid (4; 0.75 mmol), performed by following a pre-
viously reported procedure,17 gave a pale yellow gummy product;
yield: 133 mg (91%).
IR (KBr): 2834, 1514, 1462, 1038, 756 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.08–7.25 (m, 11 H), 6.83–6.81
(m, 2 H), 3.71 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 157.92, 141.43, 134.51, 134.03,
131.92, 130.81, 129.93, 129.51, 129.44, 128.09, 126.67, 126.08,
125.64, 112.31, 54.13.
HRMS (EI): m/z [M]+ calcd for C19H16OS: 292.0922; found:
292.0928.
3-Iodophenyl 2-Naphthyl Sulfide (3q)
Yellow solid; yield: 52 mg (72%); mp 86–88 °C.
IR (KBr): 1434, 1007, 744, 523 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.90 (s, 1 H), 7.83–7.75 (m, 3 H),
7.66 (s, 1 H), 7.55–7.48 (m, 3 H), 7.40 (dd, J1 = 8.8 Hz, J2 = 1.6 Hz,
1 H), 7.24 (d, J = 7.2 Hz, 1 H), 6.98 (t, J = 8.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 138.99, 138.23, 135.71, 133.78,
132.60, 131.32, 131.28, 130.65, 129.28, 129.27, 129.21, 127.84,
127.63, 126.80, 126.67, 94.87.
1-[3-(Phenylsulfanyl)phenyl]-1H-imidazole (7)
Sulfide 3k (0.3 mmol), imidazole (6; 0.3 mmol), CuI (0.04 mmol),
ligand L1 (0.04 mmol), and Cs2CO3 (0.6 mol) were added to DMF
(1 mL) in a 25-mL round-bottomed flask equipped with a stirring
bar. The mixture was stirred at 120 °C for 12 h then cooled to r.t.
H2O (5 mL) was added and the resulting mixture was extracted with
EtOAc (3 × 8 mL). The organic layers were combined, dried
(MgSO4), and concentrated under reduced pressure. The residue
was purified by silica flash column chromatography (EtOAc–petro-
leum ether, 1:3) to give a yellow gummy product; yield: 61 mg
(81%).
HRMS (EI): m/z [M]+ calcd for C16H11IS: 361.9626; found:
361.9610.
2-[(3-Iodophenyl)sulfanyl]-1,3-benzothiazole (3r)
Yellow gummy product; yield: 72 mg (90%).
IR (KBr): 1552, 1453, 1439, 1002, 750, 519 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.99 (s, 1 H), 7.81 (d, J = 8.0 Hz,
1 H), 7.23 (d, J = 8.0 Hz, 1 H), 7.61–7.55 (m, 2 H), 7.34 (t, J = 8.0
Hz, 1 H), 7.21 (t, J = 8.0 Hz, 1 H), 7.11 (t, J = 8.0 Hz, 1 H).
13C NMR(100 MHz, CDCl3): δ = 167.76, 153.72, 143.09, 139.26,
135.64, 134.11, 132.02, 131.30, 126.36, 124.70, 122.19, 120.95,
94.92.
IR (KBr): 3442, 1592, 1497, 1057, 742 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.78 (s, 1 H), 7.46 (d, J = 7.6 Hz,
2 H), 7.39–7.34 (m, 4 H), 7.23–7.17 (m, 5 H).
13C NMR (100 MHz, CDCl3): δ = 139.28, 137.46, 134.98, 132.76,
132.30, 129.99, 129.88, 129.14, 127.88, 127.59, 121.31, 118.72,
117.60.
HRMS (ESI): m/z [M + H]+ calcd for C13H9INS2: 369.9221; found:
369.9225.
4-Iodophenyl Phenyl Sulfide (3s)
Yellow gummy product; yield: 54 mg (86%).
HRMS (ESI): m/z [M + H]+ calcd for C15H13N2S: 253.0799; found:
253.0806.
IR (KBr): 1498, 1479, 1003, 810, 523 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.59 (dd, J1 = 8.0 Hz, J2 = 1.6 Hz,
2 H), 7.40 (s, 1 H), 7.37–7.24 (m, 4 H), 7.01 (dd, J1 = 8.0 Hz,
J2 = 1.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 138.86, 137.64, 136.07, 134.00,
131.55, 128.96, 127.22, 91.46.
Acknowledgment
Financial support from NSFC (no. 21202064) and sponsored pro-
jects from Jiangxi Provincial Department of Education (nos.
GJJ12211 and GJJ13245) are gratefully acknowledged.
HRMS (EI): m/z [M]+ calcd for C12H9IS: 311.9470; found:
311.9484.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
m
tgioSrantnugIifoop
r
itmnatr
4-Iodophenyl 4-Tolyl Sulfide (3t)
Yellow solid; yield: 55 mg (85%); mp 100–101 °C.
IR (KBr): 2991, 1491, 1469, 1000, 807, 517 cm–1.
References
1H NMR (400 MHz, CDCl3): δ = 7.53 (dd, J1 = 8.0 Hz, J2 = 1.6 Hz,
2 H), 7.30 (d, J = 8.4 Hz, 2 H), 7.15 (d, J = 7.6 Hz, 2 H), 6.94 (dd,
J1 = 8.0 Hz, J2 = 1.6 Hz, 2 H), 2.35 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 137.83, 137.45, 137.39, 132.46,
130.35, 129.81, 129.53, 90.55, 20.76.
HRMS (EI): m/z [M]+ calcd for C13H11IS: 325.9626; found:
325.9640.
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2977–2982

2982
Y. Liu et al.
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Synthesis 2013, 45, 2977–2982
© Georg Thieme Verlag Stuttgart · New York