Iodine-catalysed regioselective synthesis of β-hydroxysulfides

Article abstract of DOI:10.1016/j.tetlet.2017.04.043

A metal-free, and environment benign iodine-catalysed protocol has been developed for the regioselective synthesis of β-hydroxysulfides in good to excellent yields from easily accessible styrenes and thiophenols. The reaction involves single step C[sbnd]S and C[sbnd]O bonds construction.

Full text of DOI:10.1016/j.tetlet.2017.04.043

Accepted Manuscript
Iodine-catalysed regioselective synthesis of β-hydroxysulfides
Piyush Tehri, Balakrishna Aegurula, Rama Krishna Peddinti
PII:
S0040-4039(17)30485-9
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.04.043
TETL 48835
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
12 March 2017
12 April 2017
13 April 2017
Please cite this article as: Tehri, P., Aegurula, B., Krishna Peddinti, R., Iodine-catalysed regioselective synthesis of
β-hydroxysulfides, Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.04.043
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Graphical Abstract
Iodine-catalysed regioselective synthesis of β-
hydroxysulfides
Leave this area blank for abstract info.
Piyush Tehri, Balakrishna Aegurula and Rama Krishna Peddinti*

1
Tetrahedron Letters
journal homepage: www.els evier.com
Iodine-catalysed regioselective synthesis of β-hydroxysulfides
Piyush Tehri, Balakrishna Aegurula and Rama Krishna Peddinti*
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India
ARTICLE INFO
ABSTRACT
Article history:
Received
A metal-free, and environment benign iodine-catalysed protocol has been developed for the
regioselective synthesis of β-hydroxysulfides in good to excellent yields from easily accessible
styrenes and thiophenols. The reaction involves single step C−S and C−O bonds construction.
Received in revised form
Accepted
2009 Elsevier Ltd. All rights reserved.
Available online
Keywords:
Difunctionalization, C−O and C−S bond formation,
iodine catalysis, multiple bonds construction
Introduction
Previous reports:
1. Metal-catalysed C S, C O bond formation17,18
Carbon−heteroatom bond formation has a great importance in
synthetic organic chemistry because of its presence in many
natural products. Consequently, it is attracting much attention in
recent times.1 Various methods have been developed for the
synthesis of C−X bonds. However, some protocols involve
transition metals, expensive reagents or additives2 and therefore
this process is still under exploration to develop environment
friendly and affordable strategies for the construction of these
bonds.
Over the last few years, difunctionalization methodologies such
as alkoxythiolation,3 hydroxythiolation,4 acetoxythiolation,5
sulfamination6 and disulfidation7 have been performed
successfully. The generation of difunctionality in a single step is
itself a challenging task in synthetic organic chemistry. Further,
sulfide functionalization raises its importance8 as the sulphide
unit is present in numerous natural compounds.9 Sulfur-
containing organic compounds have various applications in the
area of medicinal chemistry for their antibiotic, antioxidant,
calcium channel antagonist, antimicrobial, anti-inflammatory,
antitumor, and anti-HIV activities.10 β-Hydroxysulfides act as
precursors in the synthesis of compounds having biological
importance such as pharmacophores11 including bexarotene,12
tamoxifen,13 iso-combretastin (iso CA-4),14 ratanhine,15 and in the
synthesis of β-hydroxysulfoxides which can be obtained by the
oxidation of β-hydroxysulfides using conventional oxidising
agents.16 β-Hydroxysulfides are important building blocks for the
synthesis of thioketones, allylic alcohols, cyclic sulfides,
benzothiazepines, benzoxathiepines and many other highly
functionalized organic scaffolds17 specially in the synthesis of
Leukoterin LTC4 and LTD4.
OH
OH
Zn/AlCl3, O2
S
R'S SR'
R
R
R'
R'
CH3CN/H2O, 80 o
C
AgNO3 (20 mol%)
DMF, rt
S
R
R
R'SH
2. Thiolysis of epoxides19,20
R
OH
OH
Rongalite, K2CO3
DMF, rt
S
S
O
R'S SR'
R
R
R'
R'
R
Amberlyst-15
O
R'SH
Toluene, 80 o
C
Scheme 1. Protocols for the synthesis of β-hydroxysulfides.
Several reports are available in literature for the construction of
β-hydroxysulfides (Scheme 1), which can be broadly divided in
two categories on the basis of the reactants used: i) styrenes and
⇑ Corresponding author. Tel.: +91 133 228 5438; fax: +91 13227
3560. E-mail addresses: rkpedfcy@iitr.ac.in, ramakpeddinti@gmail.com
(R.K. Peddinti).
disulfides/thiols, and ii) epoxides and disulfides/thiols. Some of
them are associated with certain drawbacks such as use of toxic
metals or solvents. Movassagh et al. synthesized β-
hydroxysulfides using styrenes and disulfides by employing
zinc/aluminium chloride as a promoter under oxygen.17 Singh et
al. synthesized β-hydroxysulfides using silver nitrate catalyst in

2
Tetrahedron
DMF.18 Later Chandrasekaran and co-workers reported the
in the presence of NCS, traces of product was observed (entry 8).
To improve the yield of the product further, the reaction was
carried out by loading iodine in 1.0 and 0.25 equivalents and 3a
was isolated in 92 and 75% yield, respectively (entries 9 and 10).
To evaluate the effect of temperature on reaction, we carried out
the reaction at different temperatures and we observed that yield
of product was dropped to 58% at 100 oC while at 60 oC yield of
product was slightly increased from 92 to 98% (entries 11 and
12). Further decrease of temperature of the reaction to 40 oC did
not provide encouraging results (entry 13). Then we screened
different solvents by using 0.5 equiv of iodine and 1:2 equiv of
thiophenol and styrene, product was obtained in traces when
DMF and ACN were used as solvents (entries 14 and 15), while
no reaction was observed when H2O was used as solvent (entry
16). Thereafter another reaction was performed in 1:1 mixture of
synthesis of β-hydroxysulfides with rongalite, potassium
carbonate in DMF19 and Lanke et. al. synthesized β-
hydroxysulfides using amberlyst-15 in toluene.20 Use of iodine as
a catalyst in oxidation reactions is one of the upcoming advances
of the recent time in terms of environmental sustainability and
cost effectiveness.21 As iodine is environmentally benign, we
envisaged that it would provide us a green path towards the
synthesis of β-hydroxysulfides.
Table 1. Optimization of reaction conditionsa
o
DMSO/H2O at 60 C and the product 3a was obtained in 50%
yield (entry 17). The optimum results were obtained when
DMSO was used as solvent. Thus the iodine (0.5 equiv) at 60 oC
in DMSO as solvent emerged as the optimal set of conditions
(entry 12) for subsequent studies.
Yield b
Reagent
(equiv)
Temp
(oC)
Entry
Solvent
(%)
1
-
80
rt
-
DMSO
DMSO
DMSO
DMSO
Table 2. Substrate scope for the synthesis of β-hydroxy-
sulfidesa
2
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
KI (0.5)
DIB (0.5)
NCS (0.5)
I2 (1.0)
I2 (0.25)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
-
3c
4d
5
80
80
80
80
80
80
80
80
100
60
40
80
80
80
51
56
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
90
6
nr
OH
OH
OH
7
nr
8
Traces
92
S
S
S
9
Br
Cl
3a (98%)
3c (69%)
(74%)
3b
10
11
12
13
14
15
16
17
75
OH
OH
OH
58
98
S
S
S
Cl
Cl
70
Cl
(63%)
OH
3d
(75%)
OH
(75%)
OH
3e
3f
Traces
Traces
nr
ACN
S
S
S
H2O
Cl
Cl
Br
F
H2O/DMSO 60
50
3g (57%)
3h (74%)
3i (70%)
aAll reactions were performed with 1a (1.0 mmol), 2a (0.5 mmol), reagent
and solvent (2 mL) on heating. bIsolated yield. nr = no reaction. c1a (0.5
OH
OH
OH
d
mmol) and 2a (0.5 mmol) were used. 1a (0.5 mmol) and 2a (1.0 mmol) were
S
S
S
F
F
F
used.
Br
Cl
(70%)
OH
3j
3k (65%)
3l (62%)
Initially the reaction was carried out with styrene (1a) and
thiophenol (2a) as model substrates in DMSO at room
o
temperature and 80 C (Table 1, entry 1). However, no reaction
OH
OH
was observed under these conditions. When 1a and 2a were
treated in the presence of iodine at room temperature the
reactants were recovered (entry 2). Later the reaction was
S
S
iPr
S
iPr
iPr
Cl
Br
o
(94%)
OH
(65%)
OH
(60%)
OH
3m
3n
3o
performed with 50 mol% of iodine in DMSO at 80 C. To our
delight β-hydroxysulfide 3a was obtained in 51% yield (entry 3).
When we performed the reaction of thiophenol with excess of
styrene (2 equiv), 3a was obtained in 90% yield (entry 5). After
that we screened different reagents such as potassium iodide,
MeO
MeO
MeO
S
S
S
iPr
MeO
Cl
diacetoxyiodobenzene
(DIB),
N-chlorosuccinimide
and
OMe
OMe
molecular iodine. When reaction was carried out in the presence
of KI and DIB, no reaction was observed (entries 6 and 7), while
(72%)
(64%)
(70%)
3p
3q
3r

3
aAll reactions were performed with a styrene 1 (0.6 mmol), a thiophenol 2
(0.3 mmol) and iodine (0.15 mmol) in DMSO (2 mL) at 60 oC.
HO
Ar'
With the optimized reaction conditions in hand, we investigated
functional group compatibility and scope of the present iodine
catalysed protocol for the synthesis of β-hydroxysulfides using a
variety of styrenes 1a-e and thiophenols 2a-d. Styrenes as well as
thiophenols both bearing electron-withdrawing and electron-
donating groups proceeded well with the present protocol. p-
S
3
Ar
SH
Ar
2
I2
HI
HI
Chlorostyrene
furnished
chlorophenyl
substituted
β-
hydroxysulfides 3e-h in yields 57–75% and p-fluoro substituted
styrene afforded the corresponding products 3i-l in 62–70% with
both electron-withdrawing and electron-donating groups on
thiophenols. The presence of bulky isopropyl group did not
affect much and the reaction proceeded well to produce the
sulfides 3m-p in 60–94% yield. To test the applicability of the
present methodology with poly-substituted styrene, the reaction
was performed with trimethoxy-styrene, and the corresponding
sulfides 3q and 3r were obtained in 64 and 70% yields. These
results indicated that the type of substituent and their bulkiness
had no regular effect on the yields of products.
I
S
O
Iodine
Catalysis
ArSI
A
Ar'
S
C
Ar
Ar'
1
To understand the mechanism, we performed a couple
of experiments using styrene (0.6 mmol), thiophenol (0.3 mmol),
iodine (0.15 mmol) in 2 mL of DMSO at 60 oC for 12 h (Scheme
2). The reaction, when carried out in the presence of TEMPO
(0.9 mmol), furnished β-hydroxysulfide 3a in traces indicating
the radical pathway of the reaction (Scheme 2a). When the
reaction was carried out under nitrogen atmosphere, it proceeded
smoothly furnishing the product in 70% yield, signifying that the
oxygen atom of the hydroxyl group is originating from the
S
Ar
Ar'
B
I
S
O
Scheme 3. Plausible reaction mechanism.
In summary, we have developed a metal-free, green and
environmentally friendly method for the synthesis of β-
hydroxysulfides in good to excellent yields from styrenes and
thiophenols using an inexpensive, nontoxic and eco-friendly
iodine/DMSO system. The iodine-mediated synthesis of various
sulfur containing compounds is under investigation in our
laboratory.
a) evidence indicating radical pathway
OH
SH
I
2
o
DMSO, 60
C
S
TEMPO, 12 h
1a
2a
General procedure for the synthesis of β-hydroxysulfide
derivatives:
3a, Traces
A mixture of a styrene (0.6 mmol), a thiophenol (0.3 mmol)
and iodine (0.15 mmol) in DMSO (2 mL) was stirred at 60 oC for
12 h. After completion of the reaction, as judged by TLC, iodine
was quenched by saturated solution of sodium thiosulphate and
the product was extracted with ethyl acetate (3×10 mL). The
combined organic phase was dried over anhydrous Na2SO4,
filtered and evaporated under reduced pressure. The resulting
crude product was purified by silica gel chromatography using a
mixture of hexanes/ethyl acetate (4:1) as eluent to afford an
analytically pure product 3.
b) evidence supporting the DMSO as oxidising agent
SH
OH
I
2
o
DMSO, 60
C
S
N
2
atmosphere, 12 h
1a
2a
3a, 70%
oxidant DMSO (Scheme 2b).
Scheme 2. Experiments supporting the mechanism.
Characterization data of selected compounds:
On the basis of our studies, a plausible reaction pathway
for the difunctionalization of styrenes is illustrated in Scheme 3.
Initially, the nucleophilic aryl thiol 2 attacks the electrophilic
iodine centre leading to the formation of intermediate ArS–I (A).
The species ArS–I liberates ArS., which reacts with electron-rich
styrene 1 to deliver a benzylic free radical intermediate B and
iodine free radical. The presence of iodine free radical makes
dimethylsulfoxide susceptible to attack at benzylic position of
intermediate B leading to the generation of intermediate C. The
attack of HI on C affords the desired β-hydroxysulfide 3 and
regenerates iodine. Though there is no direct evidence for the
formation of ArSI species, its formation from thiophenols is
suggested in the literature.9
1-Phenyl-2-(phenylthio)ethanol (3a):
Yield: 98%; IR (KBr): νmax 3445, 2925, 1583, 1404, 1330, 1121,
1
738, 700 cm–1; H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.6
−7.26 (m, 7H), 7.22−7.20 (m, 1H), 4.68 (dd,
Hz, 2H), 7.32
J =
3.6, 9.2 Hz, 1H), 3.27 (dd, J = 3.6, 13.6 Hz, 1H), 3.07 (dd, J =
9.2, 13.6 Hz, 1H), 2.98 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3) δ 142.1, 134.9, 130.1, 129.1, 128.5, 127.9, 126.7, 125.8,
71.6, 43.9 ppm.
2-(4-Chlorophenylthio)-1-phenylethanol (3b):
Yield: 74%; IR (KBr): νmax 3425, 2924, 1584, 1476, 1405, 1095,
1
1011, 700 cm–1; H NMR (400 MHz, CDCl3) δ 7.35−7.25 (m,
9H), 4.71 (dd, J = 3.2, 8.8 Hz, 1H), 3.27 (dd, J = 3.6, 13.6 Hz,
1H), 3.10 (dd, J = 9.2, 14.0 Hz, 1H), 2.80 (s, 1H) ppm; 13C NMR
(100 MHz, CDCl3) δ 141.9, 133.5, 132.8, 131.4, 129.2, 128.6,
128.1, 125.8, 71.8, 44.0 ppm.

4
Tetrahedron
(d) Xi H, Deng B, Zong Z, Lu S, Li Z. Org. Lett. 2015;17: 1180;
2-(4-Bromophenylthio)-1-phenylethanol (3c):
(e) Keshari T, Yadav VK, Srivastava VP, Yadav LDS. Green
Chem. 2014;16:3986.
Yield: 69%; IR (KBr): νmax 3427, 2922, 1582, 1473, 1387, 1090,
1063, 699 cm–1; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.8
Hz, 2H), 7.37−7.29 (m, 5H), 7.25 (d, J = 8.4 Hz, 2H), 4.71 (dd, J
= 3.6, 9.2 Hz, 1H),3.26 (dd, J = 3.6, 13.6 Hz, 1H), 3.10 (dd, J =
9.2, 13.6 Hz, 1H), 2.79 (s, 1H) ppm; 13C NMR (100 MHz,
CDCl3) δ 141.9, 132.1, 132.0, 131.6, 131.5, 128.6, 128.1, 125.8,
120.6, 71.8, 43.8 ppm.
5. Muangkaew C, Katrun P, Kanchanarugee P, Pohmakotr M,
Reutrakul V, Soorukram D, Jaipetch T, Kuhakarn C. Tetrahedron
2013;69:8847.
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(b) Wang X-R, Chen F. Tetrahedron 2011;67:4547;
(c) Usugi S-I, Yorimitsu H, Shinokubo H, Oshima K. Org. Lett.
2004;6:601;
1-Phenyl-2-(p-tolylthio)ethanol (3d):
Yield: 63%; IR (KBr): νmax 3420, 2923, 1584, 1493, 1404, 805,
(d) Matsumoto K, Fujie S, Suga S, Nokami T, Yoshida J-i. Chem.
Commun. 2009;36:5448.
8. (a) Zhou S-F, Pan X, Zhou Z-H, Shoberu A, Zou J-P. J. Org.
Chem. 2015;80:3682;
–1
1
−7.24 (m, 7H),
700 cm ; H NMR (400 MHz, CDCl3) δ 7.35
7.13 (d, J = 8.0 Hz, 2H), 4.66 (d, J = 9.6 Hz, 1H), 3.27 (dd, J =
3.2, 13.6 Hz, 1H), 3.02 (dd, J = 9.6, 14.0 Hz, 1H), 2.96−2.90 (m,
1H), 2.34 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 142.1,
137.1, 131.0, 130.8, 129.9, 128.5, 127.9, 125.8, 71.4, 44.8, 21.0
ppm.
(b) Meesin J, Katrun P, Pareseecharoen C, Pohmakotr M,
Reutrakul V, Soorukram D, Kuhakarn C. J. Org. Chem. 2016;
81:2744;
(c) Beletskaya IP, Ananikov VP. Chem. Rev. 2011;111:1596;
(d) Parumala SKR, Surasani SR, Peddinti RK. New J. Chem.
2014;38:5268.
1-(4-Chlorophenyl)-2-(phenylthio)ethanol (3e):
Yield: 75%; IR (KBr): νmax 3430, 2923, 1583, 1487, 1405, 1090,
830, 741, 692 cm–1; 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J =
8.0 Hz, 2H), 7.33−7.23 (m, 7H), 4.67 (dd, J = 3.6, 9.6 Hz, 1H),
3.27 (dd, J = 3.6, 13.6 Hz, 1H), 3.03 (dd, J = 9.2, 13.6, 1H),
2.96(s, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ 140.5, 134.4,
133.6, 130.4, 129.2, 128.6, 127.2, 127.0, 70.9, 44.1 ppm.
9. Parumala SKR, Peddinti RK. Green Chem. 2015;17:4068 and
references therein.
10. (a) Fringuelli F, Pizzo F, Tortoioli S, Vaccaro L. J. Org. Chem.
2004;69:8780;
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(c) Fringuelli F, Pizzo F, Tortoioli S, Vaccaro L. J. Org. Chem.
2003;68:8248.
1-(4-Fluorophenyl)-2-(p-tolylthio)ethanol (3l):
Yield: 62%; IR (KBr): νmax 3424, 2923, 1604, 1510, 1224, 1157,
11. Chang M-Y, Huang Y-H, Wang H-S. Tetrahedron 2016;72: 3022.
12. (a) Zhou S-F, Pan X, Zhou Z-H, Shoberu A, Zou J-P. J. Org.
Chem. 2015;80:3682;
1
491 cm–1; H NMR (400 MHz, CDCl3) δ 7.33−7.25 (m, 4H),
7.13 (d, J = 8.0 Hz, 2H), 7.01 (t, J = 8.8 Hz, 2H), 4.64 (dd, J =
(b) Surendra K, Krishnaveni NS, Sridhar R, Rao KR. J. Org.
Chem. 2006;71:5819;
−2.96 (m,
2.8, 9.2 Hz, 1H), 3.22 (dd, J = 3.2, 13.6 Hz, 1H), 3.02
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2H), 2.33 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 162.3
(d), 137.9, 137.3 , 131.2, 130.6, 130.0, 127.5 (d), 115.3 (d), 70.8,
44.9, 21.0 ppm.
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Acknowledgements
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P.T. Thanks MHRD and B.A. thanks UGC for their research
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Supplementary data
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Supplementary data associated with this article can be found, in
the online version.
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HIGHLIGHTS
Ms. Title: Iodine-catalysed regioselective synthesis of β-hydroxysulfides
•
•
•
•
•
Green protocol for the regioselective synthesis of β-hydroxysulfides.
C−S and C−O bonds construction in a single step.
Metal free reaction and no additives are required.
Reaction proceeds under aerobic conditions.
Starting materials and catalyst are inexpensive.