Ni-Catalyzed Cross-Coupling Reaction: The Direct Synthesis of Symmetrical Disulfanes from Aryl and Primary Alkyl Halides

Article abstract of DOI:10.1002/hc.21267

A novel Ni-catalyzed cross-coupling reaction is introduced for the direct synthesis of diaryldisulfanes and dialkyldisulfanes from aryl halides and primary alkyl halides at normal atmospheric conditions, respectively. This one-pot and domino protocol utilizes only 10 mol% of NiCl₂ as a catalyst and morpholin-4-ium morpholine-4-carbo-dithioate as a new, stable, solid, and odorless sulfurating reagent in the presence of ethylene glycol as a cosolvent and bidentate ligand in dimethyl formamide (DMF) at 130°C with good to excellent yields and relatively short time reaction.

Full text of DOI:10.1002/hc.21267

Heteroatom Chemistry
Volume 26, Number 5, 2015
N
i-Catalyzed Cross-Coupling Reaction: The
Direct Synthesis of Symmetrical Disulfanes
from Aryl and Primary Alkyl Halides
Mohammad Soleiman-Beigi and Zeinab Arzehgar
Department of Chemistry, Basic of Sciences FacultyIlam University, Ilam, Iran
Received 25 December 2014; revised 7 March 2015; accepted 9 March 2015
coupling reactions in the past years [2]. In many
ABSTRACT: A novel Ni-catalyzed cross-coupling re-
S-arylation reports, Pd, Cu, and Ni are most often
action is introduced for the direct synthesis of di-
used as the catalyst using catalytic and stoichiomet-
aryldisulfanes and dialkyldisulfanes from aryl halides
ric amounts of metals. Among these, Ni catalysts
and primary alkyl halides at normal atmospheric con-
are less expensive and less toxic than Pd catalysts,
ditions, respectively. This one-pot and domino pro-
more nucleophilic because of their smaller size and
tocol utilizes only 10 mol% of NiCl2 as a catalyst
more earth abundant than the Pd and Cu metals [3].
and morpholin-4-ium morpholine-4-carbo-dithioate
The S-arylation by cross-coupling reaction is much
as a new, stable, solid, and odorless sulfurating
less studied than the O-arylation and N-arylation
reagent in the presence of ethylene glycol as a co-
because of the strong coordinating properties of
solvent and bidentate ligand in dimethyl formamide
organosulfur compounds and deactivation of metal
(
DMF) at 130°C with good to excellent yields and
catalysts by sulfur-containing compounds [4]. De-
spite this, the metal-catalyzed synthesis of diaryld-
isulfanes is of current interest in organic synthesis.
Symmetrical disulfanes are found widely in many
areas such as pharmaceutical systems as proteins,
peptides, and prodrugs [5], vulcanizing agents [6],
design of rechargeable lithium batteries [7], versa-
tile reagents, synthons, and intermediate for organic
synthesis [8]. While many methods have been devel-
oped for preparing disulfanes, thiols are usually used
in the traditional methods as sulfur source reagents
relatively short time reaction. ꢀC 2015 Wiley Peri-
odicals, Inc. Heteroatom Chem. 26:355–360, 2015;
View this article online at wileyonlinelibrary.com.
DOI 10.1002/hc.21267
INTRODUCTION
A great revolution has occurred in the chemistry sci-
entific community since the development of the clas-
sical Cu-mediated Ullmann reaction. Among these
developments, the role of transition metals (Pd, Cu,
Ni, Fe, Co, Rh, and In) is most prominent in ad-
vancing the constructing of new C–C and C–X (X =
heteroatom) bonds, especially heteroatoms such as
N, O, and S [1]. Great success and salient develop-
ments have occurred in metal-catalyzed C–S cross-
[9]. These methods have some drawbacks such as the
use of expensive, toxic, and odorous thiols and un-
avoidable overoxidation of the final product. Many
disulfane formation reactions have been described
in the presence of several impressive sulfur-transfer
reagents, such as thiourea and thiouronium salts
[10], sulfated borohydride exchange resin [11], aryl-
sulfinates with hydrazine monohydrate [12], sul-
fur/sodium sulfide [13], and elemental sulfur [14],
for the direct synthesis of symmetrical disulfanes.
In our previous report, an efficient, Cu-catalyzed
symmetric diaryldisulfanes and dialkyldisulfanes
formation reaction in the presence of potassium
Correspondence to: Mohammad Soleiman-Beigi; e-mail:
SoleimanBeigi@yahoo.com; m.soleimanbeigi@mail.ilam.ac.ir.
Supporting Information is available in the online issue at
www.wileyonlinelibrary.com.
ꢀC
2015 Wiley Periodicals, Inc.
355

356 Soleiman-Beigi and Arzehgar
TABLE 1 Ligand Influence on the Reaction Conditionsa,b
FIGURE 1 Morpholin-4-ium morpholine-4-carbo-dithioate
1).
(
5
-methyl-1,3,4-oxadiazole-2-thiolate, thioacetamide,
and carbon disulfide with aryl (alkyl) halides using
0–60 mol% of Cu as catalyst was described [15].
4
Therefore, due to the dearth of general methods and
appropriate sulfur source reagents, the development
of practical, reliable, and effective methods and
reagents is an important and challenging task. In
the course of our parallel synthesis programs, we
sought to apply this methodology for Ni-catalyzed
reactions involving a catalytic amount of only 10
mol% of NiCl2 for the synthesis of symmetrical
disulfane with morpholin-4-ium morpholine-4-
carbo-dithioate (Fig. 1, 1) as a new, stable, and
odorless sulfurating reagent with aryl (primary alkyl)
halides.
Morpholin-4-ium morpholine-4-carbo-dithioate
is used as an easy to synthesize, solid, stable, low-
cost, odorless, and new sulfurating reagent for the
synthesis of symmetric disulfanes. Morpholin-4-ium
morpholine-4-carbo-dithioate can be prepared easily
in the laboratory [16]. It could be an excellent candi-
date to replace previous sulfurating reagents for the
S-arylation reaction. In this protocol, KOH is also
used as an effective, available, inexpensive, easy to
handle, and strong base. Here, we describe the first
developments in a Ni-catalyzed sulfur transfer cou-
pling methodology via domino reaction for the syn-
thesis of diaryldisulfanes and dialkyldisulfanes with
a new S-source (1) using ethylene glycol (EG) as a
cosolvent and ligand in DMF at 130°C.
aReaction conditions: Ph-I (2.0 mmol), S-source (1) (3.0 mmol),
NiCl2ꢀ6H2O (10 mol%), KOH (18.0 mmol), DMF (3.0 mL), L (20
mol%), 130°C, 24 h.
b
Isolated yields.
When DMF as a solvent was screened under the
aforementioned reaction condition without any lig-
and, the reaction proceeded, though only 25% con-
version was obtained after 24 h. Meanwhile, many
solvents such as DMSO, PEG, EG, H2O, PhMe,
EtOH, MeCN, and 1,4-dioxane were screened and
the desired results were not observed. Thus 1,10-
phenantroline, acetyl acetone, L-proline, glycine,
triphenyl phosphine, glycerol, and EG have been
employed as ligands in the cross-coupling reaction
(Table 1, L1–L7), in which EG (L5) was found to be
the best choice yielding a 63% conversion, but the
reaction not complete after 24 h.
To our delight, when the amount of EG was in-
creased to 200 mol%, the yield increased to 95%
(Table 2, entry 5). When the amount of EG was de-
creased to 150, 100, and 20 mol%, the desired prod-
uct 3a was obtained at 85, 80, and 69% yields, re-
spectively (Table 1, entries 2–4). It has been reported
that 200 mol% EG is a suitable ligand for this cross-
coupling reaction. It seemed that EG has a dual role
as a cosolvent and ligand in the cross-coupling re-
action. In the next step, solvents were screened. In
the presence of many solvents, the desired result was
not obtained (Table 2, entries 6–11).
RESULTS AND DISCUSSION
We commenced our study by investigating solvents,
ligands, catalysts, and other reaction conditions us-
ing a model reaction between the S-source (1),
iodobenzene (2a), and KOH as the base in normal
atmospheric conditions (Scheme 1).
We also employed EG as a ligand and cosolvent
to screen catalysts. The effect of the type of catalyst
was then investigated. After examination of differ-
ent Ni salts, NiCl2ꢀ6H2O was found to be the best
active catalyst species for these Ni salts (Table 3,
entry 1). Decreasing the catalyst loading to 5 mol%
of NiCl2ꢀ6H2O resulted in 49% conversion (Ta-
ble 3, entry 2). According to the results shown in
Table 3, KOH showed the efficient influence on the
SCHEME 1 Optimization of the reaction conditions.
Heteroatom Chemistry DOI 10.1002/hc

Direct Synthesis of Symmetrical Disulfanes from Aryl and Primary Alkyl Halides 357
TABLE 2 Optimization of Solvent and Amounts of Liganda
TABLE 4 Ni-Catalyzed Reaction of Aryl (Alkyl) Halides with
S-Source (1) in EG and DMF at 130°C
Entry Solvent
Ligand (mol%) Time (h) Yield (%)b
1
2
3
4
5
6
7
8
9
1
1
DMF
DMF
DMF
DMF
DMF
DMSO
–
24
24
24
12
4
25
69
80
85
95
63
5
NR
25
10
NR
EG (20)
EG (100)
EG (150)
EG (200)
EG (200)
5
1,4-Dioxane EG (200)
24
24
24
24
24
PhMe
MeCN
NMP
EG
EG (200)
EG (200)
EG (200)
EG (200)
0
1
aReaction conditions: Ph-I (2.0 mmol), S-source (1) (3.0 mmol),
NiCl2ꢀ6H2O (10 mol%), KOH (18.0 mmol), 130°C.
b
Isolated yields.
TABLE 3 Optimization of the Reaction Conditionsa
Entry Catalyst
Base
Time (h) Yield (%)b
1
2
3
4
5
6
7
8
9
1
1
NiCl
NiCl
Ni(SO
Ni(OAc)
NiNO ꢀ6H
2
ꢀ6H
ꢀ6H
2
O
O
KOH
KOH
KOH
KOH
KOH
KOH
KOH
4
95
49
30
5
c
2
2
24
24
24
15
6
24
17
24
4
)
2
ꢀ6H
ꢀ4H
2
O
O
2
2
3
2
O
42
40
d
NiCl
NiCl
NiCl
NiCl
NiCl
NiCl
2
2
2
2
2
2
ꢀ6H
ꢀ6H
ꢀ6H
ꢀ6H
ꢀ6H
ꢀ6H
2
2
2
2
2
2
O
O
O
O
O
O
e
NR
47
25
10
7
K
2
CO
3
NaOH
0
1
TBAOH 24
Et 24
3
N
aReaction conditions: Ph-I (2.0 mmol), S-source (1) (3.0 mmol), cat-
aAll the products are known compounds and were characterized by
comparison of NMR spectral data and melting points with those re-
ported in the literature.
alyst (10 mol%), base (18.0 mmol), EG (200 mol%), DMF (3.0 mL),
1
30°C.
b
Isolated yields.
c
d
e
b
5
mol% of catalyst.
Isolated yield.
At 110°C.
At 90°C.
The reaction proceeded at 90°C, though the desired
product was not obtained (Table 3, entries 6 and 7).
Having identified the optimal conditions, a range
of aryl (primary alkyl) halides (2.0 mmol) converted
to the corresponding diaryldisulfanes and dialkyld-
isulfanes in the presence of NiCl2ꢀ6H2O (10 mol%),
KOH (18.0 mmol), morpholin-4-ium morpholine-4-
carbo-dithioate (3.0 mmol), and EG (200 mol%) in
DMF at 130°C under normal atmospheric condi-
tions. Many types of aryl (primary alkyl) and hetero
aryl halides such as chlorides, bromides, and iodides
were used.
C-S coupling reaction. K2CO3, NaOH, TBAOH, and
Et3N were screened and 3a was obtained in 47,
25, 10, and 7% conversion, respectively, whereas in
the presence of 18.0, 15.0, 9.0, 6.0, and 3.0 mmol
of KOH, 3a was obtained in 95, 81, 67, 30, and
21% yield, respectively. Finally, studies screened the
effect of temperature on the reaction. The cross-
coupling reaction was carried out at 90, 110, and
130°C, respectively. It was found that the reaction
carried out at 130°C achieved 95% yield after 4 h.
As expected, decreasing the reaction temperature to
Generally, the aryl halide derivatives, bearing
both electron-poor and electron-rich groups, pro-
vide moderate to excellent yields. The highest yield of
110°C resulted in a significant drop in the reaction
rate, with 40% conversion being observed after 6 h.
Heteroatom Chemistry DOI 10.1002/hc

358 Soleiman-Beigi and Arzehgar
using Ni, as an available, stable and effective catalyst,
and a new, stable, solid and odorless morpholin-4-
ium morpholine-4-carbo-dithioate salt as the sulfu-
rating reagent.
EXPERIMENTAL
The reactions were performed under normal at-
mosphere condition. Morpholin-4-ium morpholine-
4-carbo-dithioate was prepared according to
literature methods. chemicals were purchased from
commercial suppliers, Merck and Sigma-Aldrich,
and used without further purification. Analytical
thin-layer chromatography (TLC) was performed us-
ing Merck silica gel GF254 plates. Plate chromatogra-
phy was performed using a silica gel 60 PF254+366. All
products are known and were characterized by com-
SCHEME 2 Purposed mechanism for Ni-catalyzed diaryld-
isulfane formation.
1
13
parison of their spectral ( H NMR, C NMR, and
GC-Mass) and physical data with those of authentic
95% was obtained in the cases of iodobenzene (Table
1
samples. The H-NMR spectra were recorded at 400
4, 3a). This procedure was also examined to con-
1
3
MHz and the C-NMR spectra were recorded at 100
MHz in CDCl3 or DMSO-d6 with TMS as the internal
standard. All shifts are given in ppm and all coupling
constants (J values) are reported in hertz (Hz).
vert heteroaryl halides such as 2-chlorothiophene,
-bromothiophene, and 2-iodothiophene to the
2
corresponding disulfanes; it worked with 2-
iodothiophene in good yield (Table 4, 3e). Inter-
estingly, the base (acid)-sensitive functional groups
such as carboxylic acid and amine remained un-
changed in the synthesis of corresponding diaryld-
isulfane (3i and 3j) from 2-iodobenzoic acid 2i and
General Procedures for the Synthesis of
Morpholin-4-ium Morpholine-4-carbo-
dithioate (1)
4-iodoaniline 2j (Table 4).
Morpholine (0.087 g, 1 mmol) was added to an
ethanol–water (1:1, v/v) solution and cooled in an
ice bath. Then, CS2 (0.114 g, 1.5 mmol) was added
drop wise under vigorous stirring for 5 min. The
obtained solid was filtered and recrystallized from
ethanol–water (1:1, v/v) (0.248 g, 99% yield).
However, the exact mechanism of this proto-
col is not completely clear. A plausible mecha-
nism is outlined in Scheme 2. It seems that EG
acts as a ligand and coordinates with the Ni cen-
ter, first producing complex (4) through oxida-
tive addition of Ar–X to Ni [17], and nucleophilic
addition of morpholin-4-ium morpholine-4-carbo-
dithioate (1) to the complex (4) by an Ullmann-
type reaction to yield 4-morpholinecarbodithioic
S-acid complex 5 [18]. Then, 5 was hydrolyzed
to the desired aryl thiolate in the aqueous ba-
sic conditions at high temperature (130°C) [19].
Aryl thiolate is transformed to the corresponding
diaryldisulfane under optimal reaction conditions
Morpholin-4-ium Morpholine-4-carbo-dithioate
(
1). The white solid product sublimed and decom-
posed at 222°C.
1
H NMR (400 MHz, DMSO-d6): δ = 8.61 (br, 2H),
.29 (t, J = 4.8 Hz, 4H), 3.80 (t, J = 5.0 Hz, 4H), 3.52
t, J = 4.8 Hz, 4H), 3.16 (t, J = 5.0 Hz, 4H) ppm.
4
(
1
3
C NMR (100 MHz, DMSO-d6): δ = 213.3, 66.5,
63.8, 50.3, 43.3 ppm.
AT-IR: v = 3178, 2885, 2713, 2472, 1585, 1418,
[2g, 9q].
−1
1
260, 1216, 1109, 1095 cm
.
CONCLUSIONS
General Procedures for the Synthesis of
Diaryldisulfanes and Dialkyldisulfanes
Derivatives
In conclusion, we have introduced a novel Ni-
catalyzed method for the preparation of organic
symmetric disulfanes by the domino cross-coupling
reaction of morpholin-4-ium morpholine-4-carbo-
dithioate with aryl (primary alkyl) halides in
DMF/EG system in normal atmospheric reaction
condition with good to excellent yield and short re-
action time. The important feature of this method is
To a stirred mixture of aryl (primary alkyl) halide
(2.0 mmol), morpholin-4-ium morpholine-4-carbo-
dithioate (0.75 g, 3.0 mmol) and EG (200 mol%)
in DMF (in the presence of a few drops of water)
were added to NiCl2ꢀ6H2O (10 mol%) followed by
KOH (18.0 mmol, 1.0 g) and heated at 130°C under
Heteroatom Chemistry DOI 10.1002/hc

Direct Synthesis of Symmetrical Disulfanes from Aryl and Primary Alkyl Halides 359
atmospheric conditions until completion. The
ACKNOLEDGEMENT
progress of the reaction was monitored by TLC.
Upon completion of the reaction, the mixture was
cooled to room temperature and then filtered. The
filtrate was evaporated under vacuum, ethyl acetate
Financial support from Ilam university research
council is gratefully acknowledged.
(20 ml) was added, and the mixture was washed with
REFERENCES
H2O (2 × 15 mL). The combined organic layer was
dried over Na2SO4 and filtered to afford the crude di-
aryldisulfanes and dialkyldisulfanes, which was pu-
rified by plate chromatography (silica gel, hexane:
[
1] (a) Miyaura, N.; Suzuki, A. Chem Rev 1995, 95, 2457–
2
2
483; (b) Ley, S. V.; Thomas, A. W. Angew Chem
003, 115, 5558–5607; Angew Chem, Int Ed 2003,
42, 5400–5449; (c) Evano, G.; Blanchard, N.; Toumi,
M. Chem Rev 2008, 108, 3054–3131; (d) Surry, D.
S.; Buchwald, S. L. Angew Chem 2008, 120, 6438–
ethyl acetate, 20:1; in the case of 3f and 3h was 4:1).
Diphenyldisulfane (Table 4, 3a).14 The product
6
461; Angew Chem, Int Ed 2008, 47, 6338–6361; (e)
Phapale, V. B.; Cardena, D. J. Chem Soc Rev 2009,
8, 1598–1607; (f) Hartwig, J. F. Acc Chem Res 2008,
was obtained (hexane–ethyl acetate, 20:1) as a white
1
solid in 95% yield. mp = 59–60°C. H NMR (400
3
MHz, CDCl3): δ = 7.24–7.36 (m, 6H), 7.54 (m, 4H)
41, 1534–1544.
1
3
[
2] (a) Beletskaya, I. P.; Cheprakov, A. V. Coord Chem
Rev 2004, 248, 2337–2364; (b) Basu, B.; Mandal, B.;
Das, S.; Kundu, S. Tetrahedron Lett 2009, 50, 5523–
ppm. C NMR (100MHz, CDCl3): δ = 137.0, 129.1,
1
27.5, 127.2 ppm. Elemental analysis calculated for
C12H10S2: % = C, 66.01; H, 4.62; S, 29.37. Found: C,
6.49; H, 4.47; S, 29.96. GC-Mass (EI): m/z = 218.0
M+].
Bis(4-methoxyphenyl)disulfane (Table 4, 3c).14
The product was obtained (hexane–ethyl acetate,
0:1) as a white solid in 51% yield. mp = 41–43°C.
5
4
528; (c) Sengupta, D.; Basu, B. Med Chem Lett 2014,
, 17; (d) Beletskaya, I. P.; Ananikov, V. P. Chem Rev
6
[
2011, 111, 1596–1636; (e) Zhang, Y.; Ngeow, K. C.;
Ying, J. Y. Org Lett 2007, 9, 3495–3498; (f) Gendre,
F.; Yang, M.; Diaz, P. Org Lett 2005, 7, 2719–2722;
(
g) Jammi, S.; Barua, P.; Rout, L.; Saha, P.; Punniya-
murthy, T. Tetrahedron Lett 2008, 49, 1484–1487;
h) Lee, C.-F.; Liu, Y.-C.; Badsara, S. S. Chem Asian
2
1
H NMR (400 MHz, CDCl3): δ = 7.31 (d, 4H), 6.87 (d,
(
4
H), 3.82 (s, 6H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 159.0, 132.8, 127.4, 114.7, 55.4 ppm. Elemental
analysis calculated for C14H14O2S2: % = C, 60.40;
H, 5.07; S, 23.04. Found: C, 60.04; H, 5.70; S, 22.84;
GC-Mass (EI) m/z = 278.1 [M+].
J 2014, 9, 706–722.
[
[
3] (a) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.;
Zhang, N.; Resmerita, A. M.; Garg, N. K.; Percec, V.
Chem Rev 2011, 111, 1346–1416; (b) Han, F.-S. Chem
Soc Rev 2013, 42, 5270–5298.
4] (a) Kondo, T.; Mitsudo, T. Chem Rev 2000, 100, 3205–
3220; (b) Reddy, V. P.; Kumar, A. V.; Swapna, K.; Rao,
K. R. Org Lett 2009, 11, 1697–1700.
1
4
Bis(4-nitrophenyl)disulfane (Table 4, 3f). The
product was obtained (hexane–ethyl acetate, 4:1) as
1
[5] (a) Kanada, Y.; Fukuyama, T. J. Am Chem Soc 1993,
a yellow solid in 40% yield. mp = 173–175°C. H
1
2
2
15, 8451–8452; (b) Tian, X.; Wickstrom, E. Org Lett
002, 4, 4013–4016; (c) Bulaj, G. Biotechnol Adv
005, 23, 87–92; (d) Hekmatshoar, R.; Sajadi, S.;
NMR (400 MHz, CDCl3): δ = 8.14 (d, 4H), 6.62 (d,4H)
1
3
ppm. C NMR (100 MHz, CDCl3): δ = 155.4, 138.1,
1
27.1, 113.8 ppm.
Heravi, M. M.; Bamoharram, F. Molecules 2007, 12,
223–2227; (e) Ruano, J. L. G.; Parra, A.; Aleman, J.
Bis(4-aminophenyl)disulfane (Table 4, 3i).15 The
2
Green Chem 2008, 10, 706–711; (f) Kapanda, C. N.;
Muccioli, G. G.; Labar, G.; Poupaert, J. H.; Lambert,
D. M. J Med Chem 2009, 52, 7310–7314; (g) Zhang,
L.; Chou, C. P.; Moo-Young, M. Biotechnol Adv 2011,
29, 923–929; (h) Caldarelli, S. A.; Hamel, M.; Duckert,
J. F.; Ouattara, M.; Calas, M.; Maynadier, M.; Wein,
S.; P e´ rigaud, C.; Pellet, A.; Vial, H. J.; Peyrottes, S. J
Med Chem 2012, 55, 4619–4628; (i) Postma, T. M.;
Albericio, F. Eur J Org Chem 2014, 2014, 3519–3530.
6] (a) Christoforou, A.; Nicolaou, G.; Elemes, Y. Tetra-
hedron Lett 2006, 47, 9211–9213; (b) Ramadas, K.;
Srinivasan, N. Synth Commun 1995, 25, 227–234; (c)
Fisher, H. L. Ind Eng Chem 1950, 42, 1978–1982.
7] Maddanimath, T.; Khollam, Y. B.; Aslam, M.; Mulla,
I. S.; Vijayamohanan, K. J. Power Sources 2003, 124,
product was obtained (hexane–ethyl acetate, 4:1) as
1
3
a yellow solid in 65% yield. mp = 75–77°C. C NMR
100 MHz, CDCl3): δ = 155.6, 129.7, 120.7, 115.4
ppm. FT-IR: v = 3427, 3354, 3213, 3034, 1604, 1497,
(
−1
1
276, 1174 cm
Bis(2-carboxyphenyl)disulfane (Table 4, 3j).
The product was obtained (hexane–ethyl acetate,
.
1
4
4
2
8
:1) as a white solid in 96% yield. mp = 283–
[
[
1
85°C. H NMR (400 MHz, CDCl3): δ = 13.58 (s, 2H),
.04 (d, J = 7.6 Hz, 2H), 7.60 (m, 4H), 7.35 (t, J = 6.8
1
3
Hz, 2H) ppm. C NMR (100 MHz, CDCl3): δ = 168.1,
1
39.4,133.8,132.1,128.5,126.5,125.5ppm. FT-IR:v=
1
−
3541–3321,1680, 1575, 1472, 1297, 1266, 1043 cm
.
1
33–142.
1
4
Dibenzyldisulfane (Table 4, 3k). The product
[8] (a) Nishiyama, Y.; Maehira, K.; Nakase, J.; Son-
oda, N. Tetrahedron Lett 2005, 46, 7415–7451;
(b) Taniguchi, N. J Org Chem 2006, 71, 7874–7876;
was obtained (hexane–ethyl acetate, 20:1) as a white
1
solid in 88% yield. mp = 68–70°C. H NMR (400
(
(
c) Taniguchi, N. J Org Chem 2007, 72, 1241–1245;
d) Fukuzawa, S.-I.; Shimizu, E.; Atsuumi, Y.; Haga,
MHz, CDCl3): δ = 3.63 (s, 4H), 7.28–7.38 (m, 10H)
1
3
ppm. C NMR (100 MHz, CDCl3): δ = 137.4, 129.5,
M.; Ogata, K. Tetrahedron Lett 2009, 50, 2374–2376;
(e) Alves, D.; Lara, R. G.; Contreira, M. E.; Radatz, E.
128.5, 127.5, 43.3 ppm.
Heteroatom Chemistry DOI 10.1002/hc

360 Soleiman-Beigi and Arzehgar
S.; Duarte, L. F. B.; Perin, G. Tetrahedron Lett 2012,
Bennett, B. L.; Steinberg, S. M. Synth Commun 2005,
35, 631–638.
5
3, 3364–3368.
[
9] (a) Shcherbakova, I.; Pozharskii, A. F. In Compre-
hensive Organic Functional Group Transformations
II; Katritzky, A. R.; Taylor, R.; Ramsden, Ch. (Eds.);
Pergamon: Oxford, UK, 2004; Vol. 2, pp. 210–233; (b)
Bulman Page, P. C.; Wilkes, R. D.; Reynolds, D. In
Comprehensive Organic Functional Group Transfor-
mations; Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W.
[11] Bandgar, B. P.; Uppalla, L. S.; Sadavarte, V. S. Tetra-
hedron Lett 2001, 42, 6741–6743.
[12] Zhu, R.-H.; Shi, X.-X. Synth Commun 2012, 42, 1108–
1114.
[13] (a) Sonavane, S. U.; Chidambaram, M.; Almog, J.;
Sasson, Y. Tetrahedron Lett 2007, 48, 6048–6050; (b)
Wang, J.-X.; Gao, L.; Huang, D. Synth Commun 2002,
32, 963–969.
[14] (a) Li, Z.; Ke, F.; Deng, H.; Xu, H.; Xiang,
H.; Zhou, X. Org Biomol Chem 2013, 11, 2943–
2946; (b) Chen, H-Y.; Peng, W.-T.; Lee, Y.-H.;
Chang, Y.-L.; Chen, Y.-J.; Lai, Y.-C.; Jheng, N.-Y.;
Chen, H-Y. Organometallics 2013, 32, 5514–5522; (c)
Chatterjee, T.; Ranu, B. C. RSC Adv 2013, 3, 10680–
10686.
[15] (a) Soleiman-Beigi, M.; Mohammadi, F. Tetrahedron
Lett 2012, 53, 7028–7030; (b) Soleiman-Beigi, M.;
Hemmati, M. Appl Organometal Chem 2013, 27, 734–
736; (c) Soleiman-Beigi, M.; Izadi, A. J Chem 2013,
ID 725265, 1–5.
(
1
Eds.); Pergamon: Oxford, UK, 1995; Vol. 2, pp. 177–
87; (c) Sato, R.; Kimura, T. In Science of Synthesis,
Kambe, N.; Drabowicz, J.; Molander, G. A. (Eds.);
Thieme: Stuttgart , Germany, 2007; Vol. 39, pp. 573–
5
88 (available also on line); (d) Mandal, B., Basu,
B., RSC Adv, 2014, 4, 13854–13881; (e) Demkowicz,
S.; Rachon, J.; Witt, D. Synthesis 2008, 2033–2038;
(
4
f) Ali, M. H.; McDermott, M. Tetrahedron Lett 2002,
3, 6271–6273; (g) Leino, R.; Lonnqvist, J.-E. Tetrahe-
dron Lett 2004, 45, 8489–8491; (h) Ozen, R.; Aydin, F.
Monatsh Chem 2006, 137, 307–310; (i) Christoforou,
A.; Nicolaou, G.; Elemes, Y. Tetrahedron Lett 2006,
4
7, 9211–9213; (j) Hunter, R.; Caira, M.; Stellenboom,
N. J Org Chem 2006, 71, 8268–8271; (k) Silveira, C. C.;
Mendes, S. R. Tetrahedron Lett 2007, 48, 7469–7471;
[16] (a) Mafud, A. C.; Sanches, E. A.; Gambardella, M.
T. Acta Cryst 2011, E67, o2008; (b) Carta, F.; Aggar-
wal, M.; Maresca, A.; Scozzafava, A.; McKenna, R.;
Masini, E.; Supuran, C. T. J Med Chem 2012, 55,
1721–1730.
(
l) Kabalka, G. W.; Reddy, M. S.; Yao, M.-L. Tetrahe-
dron Lett 2009, 50, 7340–7342; (m) Vandavasi, J. K.;
Hu, W.-P.; Chen, C.-Y.; Wang, J.-J. Tetrahedron 2011,
6
7, 8895–8901; (n) Basu, B., Sengupta, D. Tetrahe-
[17] (a) Desmarets, C.; Schneider, R.; Fort, Y. J Org Chem
2002, 67, 3029–3036; (b) Gao, C.-Y.; Yang, L.-M. J
Org Chem 2008, 73, 1624–1627.
dron Lett 2013; 54, 2277–2281; (o) Soleiman-Beigi,
M.; Taherinia, Z. Monatsh Chem 2014, 145, 1151–
1
154; (p) Witt, D.; Klajn, R.; Barski, P.; Grzybowski,
[18] (a) Liu, Y.; Bao, W. Tetrahedron Lett 2007, 48, 4785–
4788; (b) Bhadra, S.; Saha, A.; Ranu, B. C. Green
Chem 2008, 10, 1224–1230.
B. A. Curr Org Chem 2004, 8, 1763–1797; (q) Saxena,
A., Kumar, A., Mozumdar, S. J Mol Catal A: Chem
2
007, 269, 35–40.
[19] (a) Akkilagunta, V. K.; Kakulapati, R. R. J Org Chem
2011, 76, 6819–6824; (b) Prasad, D. J. C.; Sekar, G.
Org Lett 2011, 13, 1008–1011.
[
10] (a) Firouzabadi, H.; Iranpoor, N.; Abbasi, M. Tetra-
hedron Lett 2010, 51, 508–509; (b) Emerson, D. W.;
Heteroatom Chemistry DOI 10.1002/hc