Iodine(III) Enabled Dehydrogenative Aryl C?S Coupling by in situ Generated Sulfenium Ion

Article abstract of DOI:10.1002/adsc.201801510

Due to the normal polarity preferences, arenes form stable complexes with thiols through S?H???π interaction and direct dehydrogenative aryl C?S coupling is usually restricted. We report here an umpolung based one pot and direct C?S coupling approach unde

Full text of DOI:10.1002/adsc.201801510

Title: Iodine(III) Enabled Dehydrogenative Aryl C-S Coupling by in situ
Generated Sulfenium Ion
Authors: Khokan Chowdhuri, saikat maiti, and Prasenjit Mal
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801510
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iodine(III) Enabled Dehydrogenative Aryl C-S Coupling by in
situ Generated Sulfenium Ion
Khokan Choudhuria, Saikat Maitia and Prasenjit Mala,*
a
School of Chemical Sciences, National Institute of Science Education and Research (NISER), HBNI, Bhubaneswar,
PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India, E-mail: pmal@niser.ac.in
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Due to the normal polarity preferences, arenes
form stable complexes with thiols through S–H∙∙∙π
interaction and direct dehydrogenative aryl C-S coupling is
usually restricted. We report here an umpolung based one
pot and direct C-S coupling approach under metal free and
mild condition. Electrophile sulfenium ions were generated
in situ from thiols using iodine(III) reagent PhI(OAc)2
(PIDA) and subsequently used for aromatic electrophilic
substitution (EArS) to synthesize diaryl sulfides. Also by
using of appropriate amount of PIDA, cascaded synthesis of
C-S and S=O bonds led to aryl sulfinyl arenes in one pot.
Covalent self-sorting or competitive experiments further
confirmed the involvement of sulfenium ion in the EArS.
Keywords: C-S Coupling; Diaryl Sulfides; Diaryl
Sulfoxide; Iodine(III); Sulfenium ion
radical pathway, using strong oxidants, with electron
rich systems, etc.[14]
Introduction
The C-S bond formation reactions have received
significant interest because organosulfur compounds
are found in many natural products, biological and
pharmaceutical compounds.[1] Nexium, provigil,
nelfinavir,[2] AZD4407[3] etc. are some notable sulfur
containing drug molecules. Several sulfides and aryl
sulfoxides are also known to be used as HIV-1
integrase inhibitor, antidepressant, anticancer,
antifungal, antibacterial, anti-tumor activities, etc.[4]
For many years, synthesis of C-S bonds[5] were
usually based on the transition metal catalyzed cross
couplings[6] of aryl halides with thiophenols.[7] The
metal catalyzed C-S coupling strategy are known in
which directing group (DG) or template mediated
synthesis of diaryl sulfides are mainly reported.[8]
Similarly, Ni, Co, Pd, or Cu metal catalyzed coupling
reactions of aryl halides or template assisted synthesis
are described in Figure 1b and Figure 1c,
respectively.[9]
Aryl
sulfenylation[10]
and
sulfoxidation under photocatalytic condition have
also recently been developed but the method contains
drawback such as use of thiosulfate salts.[11] However,
among metal free methods,[12] most of the coupling
reactions are reported via prefunctionalization of the
substrates.[13] Therefore, dehydrogenative coupling
reactions via non-requirement of prefunctionalized
substrates are mostly desirable, for example our
present approach is shown in Figure 1a. In addition,
majority of the known literatures are based on via
Figure 1. Literature known approaches for Aryl C-S
coupling: a) Aryl halides were used as one of the coupling
partners. b) Template assisted synthesis. c) This work:
under metal free and mild condition, selective synthesis of
either diaryl sulfides or sulfoxides by choosing appropriate
amount of PIDA.
1
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
Many chemical reactions are well known to be
controlled by weak interactions.[15] Towards
development of newer materials on demand with
suitable functionality can be introduced by choosing
appropriate
non-covalent
or
supramolecular
interactions. Selective examples of the weak
interactions like anion-π,[16] cation-π,[17] charge-
transfer,[18] halogen bonding,[19] hydrophobic
effect,[20] etc. are popularly used in organic synthesis.
Thus the approach on small molecules system
[21]
chemistry
became popular research topic of
interest to design molecules of demand using those
cooperative[22] multiple weak interactions[23] in the
area of supramolecular catalysis.[24] Recently, the
newly identified S–H∙∙∙π interaction[25] is also gaining
popularity in the organic synthesis.[26]
In continuation of our research focus towards the
use of hypervalent iodine reagents in organic
synthesis,[27] herein we report an intermolecular
dehydrogenative aryl C-S coupling reaction[28] for the
synthesis of diaryl sulfides and aryl sulfinyl arenes
(or diaryl sulfoxides) from the respective arenes and
thiophenols via generation of sulfenium ion. Both the
reactions could be performed selectively in one pot
by choosing the appropriate amount of iodine(III)
reagent phenyliodine diacetate PhI(OAc)2 or PIDA
(Figure 1a). The synthesis of diaryl sulfoxide is
developed based on cascaded C-S and S=O bond
formation in one pot using 3.0 equiv of PIDA at 4 h
under ambient condition (Figure 1a)
Figure 2. a) Normal-polarity preferences inhibit C-S
coupling reaction due to S–H∙∙∙π interaction. b) Umpolung
approach towards dehydrogenative aryl C-S cross coupling
via sulfenium ion.
Table 1. Condition Optimization.
Results and Discussion
Due to normal polarity preferences the π-electrons of
arenes and hydrogens of thiols prefer hydrogen
bonding or S–H∙∙∙π interaction,[25, 26b, 29] which inhibit
direct aryl C-S coupling (Figure 2a). However, using
umpolung reactivity of sulfur, we have shown here
that direct C-S coupling was possible via generation
of sulfenium ion[12b] and subsequent utilization of
them for aromatic electrophilic substitution (EArS)
reactions (Figure 2b). The sulfenium ion can be
considered as the sulfur analogue of carbenium[30] or
nitrenium ions[30-31] and are generally prepared by
activation of S-arylthiophthalimides.[12, 32] However,
we have shown here that no prefunctionalization of
the substrates or any template approach were
necessary for this cross dehydrogenative C-S
coupling reaction of arenes and thiols, and the
sulfenium ions could be generated in situ by
oxidation of thiols. Unprecedentedly, we report here
the generation of sulfenium ion using hypervalent
iodine(III) reagents. In a typical reaction condition
PhI(OAc)2 (PIDA) was used as the only reagent in
1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solvent and
the reactions could be done at room temperature and
open atmosphere condition. Overall, it is
demonstrated that within a same reaction system, the
normal preference of thiophenol-arene reaction could
be switched to umpolung using iodine(III) reagent
PIDA.
entry
1
oxidant
(1.0 equiv)
PIDA
solvent
yield (%)a
85
HFIP/DCM
(1:1)
HFIP
DCM
EtOH
CH3CN
H2O
HFIP
DMSO
HFIP
HFIP
TFE
2
3
4
5
6
7
8
9
PIDA
PIDA
PIDA
PIDA
PIDA
I2
99 (96)b
9
15
31
38
NIL
NIL
90
62
48
I2
PhI(OPiv)2
PIFA
PIFA
10
11
aNMR Yields; bIsolated yields
Towards optimization of the reaction condition,
mesitylene (1a) and 4-bromo-thiophenol (2a) were
used as model substrates (Table 1). When equimolar
mixture of 1a and 2a were treated with 1.0 equiv of
PIDA in various solvents at ambient condition, the
desired product (4-bromophenyl)(mesityl)sulfane
(3aa) was isolated (Table 1). Among the solvents
examined, HFIP was found to be the most efficient
(entry 2-6). Interestingly, molecular iodine in
solvents like HFIP (entry 7) and DMSO (entry 8) led
2
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
to disulfide as the only product and no desired
product was obtained. However, use of oxidants other
than PIDA e.g., PhI(OPiv)2 (entry 9) and
PhI(OCOCF3)2 (entry 10-11) led to inferior results.
witnessed by using m-xylene (3hf), 2-bromo-
mesitylene (3gb), and anisole (3de). It is also noticed
that –CHO group containing electron rich arene also
worked well to afford the desired product 3lb with
90% yield. More interestingly, two consecutive C-S
bonds formation was possible during the reaction
between thiophenol and 1,4-dimethoxybenzene to
produce 3ib. On the other hand when heterocycles
were used as arenes under standard condition (Figure
3c), indole led to 41% yield of the product 3mb,
however, benzofuran and coumarin didn’t respond to
the reaction condition. The X-ray structure of the
compound 3af is shown in Figure 3a.[33]
Figure 4. Control experiments. a) TEMPO radical
experiment established that the reaction proceeded via non-
radical pathway. b) Disulfide formation was observed in
absence of arene nucleophile. c) Sulfenium ion was
generated from disulfide for the EArS. d) Alkyl thiols also
led to the successful generation of sulfenium ions.
Figure 3. Substrate scope for the dehydrogenative C-S
coupling reaction (isolated yields). a) C-S coupled
products from mesitylene with various thiols. b) Different
kinds of arenes were also reacted. c) Attempted reactions
from heterocycles.
Control experiments shown in Figure 4 helped to
rationalize that the reaction proceeded via the
sulfenium ion (vide supra, Figure 2b). At standard
condition, addition of radical scavenger TEMPO
(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl) could not
inhibit the product formation and 3aa was isolated
with 44% yield (Figure 4a). The TEMPO radical is
also well known to oxidize the thiols to disulfides via
homo-coupling.[34] This confirms that the reaction did
not follow the radical pathway. When the thiol 2a
was treated with PIDA, disulfide 5aa was obtained as
the only product (Figure 4b). This was another
confirmation that the reaction proceeded via
sulfenium ion. Possibly, the sulfenium ion could react
with available nucleophile thiols for the S-S bond
formation. In addition, one of the disulfides (5bb)
was oxidized to the sulfenium ion[35] using the PIDA
and in presence of mesitylene, product 3aa could be
Using the optimized condition, a range of thiols and
arenes were reacted to explore the scope of the
coupling reactions (Figure 3). A series of thiophenols
bearing electron-withdrawing groups like halogen
(3aa, 3ac, 3ad, 3ai, 3aj, 3ba, 3ca and 3da), nitro
(3ag), trifluoromethyl (3ah) as well as electron-
donating substituents such as alkyl (3ae, 3de), alkoxy
(3af, 3hf) were fair-yielding to produce C-S coupled
products. The formation of diarylsulfides from alkoxy
(3ba, 3ca, 3da, 3eb, 3lb, 3ib, 3de) as well as alkyl
(3fb, 3gb, 3hf) substituted arenes were also found to
be compatible to this methodology. A single
regioisomer was formed when either 3,5-dimethyl
anisole (3eb) or 1,3-dimethyl-5-tert-butylbenzene
(3fb) was used as arene source for the coupling
reaction. Relatively lower yield of products was
3
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
isolated in 80% yield (Figure 4c). We anticipated that
the EArS reaction proceeded via the generation of
sulfenium ion and isolation of aryl C-S coupled
products with alkyl thiols (Figure 4d) also supported
for the formation sulfenium ion. The use of
fluorinated solvents to perform hypervalent iodine
mediated reactions are well established in
literature.[36] So, it is expected that being non-
nucleophilic and highly polar in nature, the solvent
HFIP could also stabilize the cationic intermediate.[37]
are difficult and known via multistep methodology.[41]
Herein the synthesis of various sulfoxides are being
reported under mild condition (Figure 6). A wide
range of aromatic thiols were treated with various
arenes in presence of 3.0 equiv of PIDA in HFIP at
room temperature to afford the aryl sulfinyl arenes in
good to excellent yields. Electron withdrawing
groups such as halogens (4aa, 4aj), trifluoromethyl
(4ah), electron donating methoxy (4af, 4hf) or
unsubstituted thiophenols (4ab, 4bb, 4fb, 4jb, 4db,
4kb) underwent smooth conversion towards the
generation of sulfoxides with moderate to excellent
yields. Additionally, using aliphatic thiol also we
could isolated the desired product 4al with good yield
(66%). Also, a wide range of electron donating arenes
such
as
mesitylene,
m-xylene,
1,3,5-
3,5-
3-
trimethoxybenzene,
1,3,5-triethylbenzene,
dimethyl-tert-butyl-benzene,
anisole,
phenoxytoluene were tested for the coupling reaction.
Exclusive regioselectivity was observed in products
4hf, 4fb, 4db, 4kb. The X-ray structure of the
compound 4aa is shown in Figure 6.[33]
Figure 5. The competitive experiments. EArS in the
covalent self-sorting via sulfenium ion. The product
selectivity was observed due to relative nucleophilicity of
arenes. Therefore, it was found that mesitylene was better
nucleophile than a) anisole and b) m-xylene, and inferior
than 3,5-dimethylanisole.
The self-sorting[38] or competitive experiments shown
in Figure 5 were performed to prove that the
sulfenium ion was one of the intermediates in the
reaction. Once the sulfenium ion was generated in
situ, the nucleophilicity of arenes was controlling
factor for the product selection process within the
system via
a
covalent self-sorting.[39] Herein,
mesitylene as a better nucleophile than anisole,
afforded greater selectivity towards the product
formation (Figure 5a). Similarly, when 1.1 equiv of
PIDA and thiophenol (1.0 equiv) were reacted with
1:1 mixture of mesitylene and m-xylene, 3ae (only
mesitylene reacted) was obtained exclusively (Figure
5b). Likewise, 3,5-dimethyl anisole being a better
nucleophile led to the selective formation of the 3ee
(Figure 5c) and no mesitylene adduct could be
isolated. Thus rationalized that the product selectivity
was the outcome due to the relative nucleophilicity of
arenes towards sulfenium ion intermediate for the
EArS reaction.
Figure 6. Synthesis of aryl sulfinyl arenes or diaryl
sulfoxides. The reaction possibly proceeded by two steps
in cascaded manner: first diaryl sulfides formation via
EArS of sulfenium ions and followed by oxidation at the
sulfur center with the help of PIDA.
Furthermore, a plausible mechanism for the synthesis
of aryl sulfinyl arenes or diaryl sulfoxides is shown in
Figure 7. Initially, 1.0 equiv of PIDA was required to
obtain diaryl sulfides (Figure 7a). Secondly, these
diaryl sulfides further reacted with PIDA to produce
the diaryl sulfoxides (Figure 7b). Possibly, HFIP
helped to ionize PIDA to acetoxy(phenyl)iodinium
cation 5 and HFIP coordinated acetate anion
intermediate 6. Following, nucleophilic attack by
diaryl sulfide to cation 5 led to intermediate 7 which
was further converted to 8 with the help of acetate
The C-S coupling methodology was further
extended to the cascaded C-S and S=O bond
formation reaction starting from the arenes and thiols,
towards one pot synthesis of diaryl sulfoxides (Figure
6).[40] The direct synthesis of sulfoxides[4] from thiols
4
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
anion. Second molecule of acetate anion again
produce the desired product 4. Overall, during the
formation of 4 from 7, involvement of acetate anion
was more than once. As a result slight excess of
PIDA was required. We have also observed that
under standard condition, 2.5 equiv of PIDA led to
~85% of the diaryl sulfoxide derivatives (4aa). Thus,
in order to avoid any discrepancy of the yield of final
product, 3.0 equivalent of PIDA was used.
by controlled use of PIDA. We anticipate that this
unprecedented work might find suitable applications
in the research area of supramolecular catalysis in
organic chemistry.
Experimental Section
Instrumentation and Chemicals
All the chemicals were purchase from commercial source
and used as received. All the reactions were carried out in
an open atmosphere condition. Column chromatographic
purification was performed using silica gel (Mesh 230-
400) and ethyl acetate/hexane as eluent unless otherwise
specified. Thin-layer chromatography (TLC) was
performed on Merck silica gel 60 F254 aluminium plate and
visualized with UV lamp (254 nm). 1H and 13C NMR
spectra of the compounds were recorded on either 400 or
o
700 MHz spectrometer at 25 C. The chemical shift value
in ppm (δ) were reported with respect to the residual
1
chloroform (7.26 for H and 77.16 ppm for 13C). Infrared
(IR) spectra were recorded in wave number (cm-1). Digital
melting point apparatus were used to record the melting
point of the compound. High resolution mass spectroscopy
(HRMS) was recorded on ESI-TOF (Time-of-flight) mass
spectroscopy.
Synthesis
Representative procedure for the preparation of (4-
Bromophenyl)(mesityl)sulfane (3aa). To the stirring
solution of 4-bromo thiophenol (2a, 60 mg, 0.317 mmol)
and mesitylene (1a, 88 μL, 0.635 mmol) in 1,1,1,3,3,3-
Figure 7. Plausible mechanism for the synthesis of diaryl
sulfoxide. a) PIDA was required as 1.0 equiv for the
synthesis of diaryl sulfides. b) Diaryl sulfides further
reacted with PIDA to produce the diaryl sulfoxides.
hexafluoro-2-propanol
(HFIP),
PIDA
(Diacetoxy
phenyliodide) (102 mg, 0.317 mmol) were added slowly at
room temperature then the resulting solution were stirred
for 30 min under open atmosphere. After the completion of
reaction resulting solution was evaporated to dryness. The
crude residue was purified on silica gel column
chromatography using hexane and ethyl acetate as eluent
to obtain 3a (94 mg off white solid, 0.306 mmol, yield
96%).
Gram scale synthesis of 3ab was achieved by using
1.3 g (10.8 mmol) of 1a and 2.4 g (21.6 mmol) of 2b
under standard condition and 2.22 g of 3ab was
obtained (Figure 8).
Representative procedure for the preparation of 2-((4-
Bromophenyl)sulfinyl)-1,3,5-trimethylbenzene (4aa). In
a 10 mL round bottom flask, charged with 4-bromo
thiophenol (2a, 60 mg, 0.317 mmol) and mesitylene (1a,
111 μL, 0.793 mmol) in HFIP, then PIDA (307 mg, 0.952
mmol) was added and the resulting solution were stirred
for 4 hour at room temperature under open atmosphere.
After completion, the solvent was evaporated to dryness
under reduced pressure and the crude reaction mixture was
purified with silica gel column chromatography using ethyl
acetate, hexane mixture as an eluent to get 4aa (96 mg,
0.297 mmol, yield 94%).
Figure 8. Gram scale synthesis of 3ab.
General procedure for the self-sorting experiment. In a
round bottom flask charged with 4-methyl benzenethiol (2e,
60 mg, 0.483 mmol) in HFIP corresponding two arene
molecules (1.0 equiv each) were added to the solution.
After that PIDA (172 mg, 0.531 mmol) were added slowly
at room temperature and the resulting solution were stirred
for 45 min under open atmosphere. Then the mixture was
concentrated under reduced pressure and dried over high
vacuum to record the NMR spectrum.
Conclusion
In summary,
a
unique protocol for the
dehydrogenative aryl C-S coupling is demonstrated
by understanding the role of weak interactions in the
reactions. Within a system, reactivity of the
thiophenol-and arenes could be switched from normal
polarity preferences to umpolung using iodine(III)
reagent PIDA. Thus, EArS reaction was performed
towards making the aryl C-S bond by in situ
generation of sulfenium ions. The competitive
experiments also supported for involvement of
sulfenium ion intermediate. The same coupling
protocol was further extended for one step synthesis
of aryl sulfinyl arenes directly from arenes and thiols
(4-Bromophenyl)(mesityl)sulfane (3aa):[3] Rf = 0.85
(Hexane); off white solid; yield 96% (94 mg); mp 96 - 100
ºC; 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J = 8.6 Hz, 2H),
7.03 (s, 2H), 6.79 (d, J = 8.6 Hz, 2H), 2.38 (s, 6H), 2.34 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 143.8, 139.8, 137.9,
131.9, 129.6, 127.1, 126.5, 118.0, 21.8, 21.3.
Mesityl(phenyl)sulfane (3ab):[3] Rf = 0.9 (Hexane);
Colourless liquid; yield 97% (120 mg); 1H NMR (400
MHz, CDCl3) δ 7.18 (t, J = 7.6 Hz, 2H), 7.06 (d, J = 7.4
5
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10.1002/adsc.201801510
Advanced Synthesis & Catalysis
Hz, 1H), 7.02 (s, 2H), 6.93 (d, J = 7.6 Hz, 2H), 2.39 (s,
6H), 2.33 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 143.9,
139.4, 138.5, 129.5, 129.0, 127.1, 125.6, 124.6, 21.8, 21.3;
HRMS (ESI-TOF) calcd for C15H16S (M)+ 228.0967, found
228.0956.
Ethyl(mesityl)sulfane (3ak):[3] Rf
=
0.9 (Hexane);
Colourless liquid; yield 68% (104 mg); 1H NMR (400
MHz, CDCl3) δ 6.97 (s, 2H), 2.69 (q, J = 7.4 Hz, 2H), 2.55
(s, 6H), 2.30 (s, 3H), 1.22 (t, J = 7.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 143.1, 138.0, 130.1, 129.0, 29.5, 22.1,
21.1, 15.0.
(4-Chlorophenyl)(mesityl)sulfane (3ac):[42] Rf = 0.85
(Hexane); white solid; yield 87% (95 mg); mp 78 – 80 ºC
(lit.[7b] 74 – 75 ºC); 1H NMR (400 MHz, CDCl3) δ 7.14 (d,
J = 8.6 Hz, 2H), 7.02 (s, 2H), 6.84 (d, J = 8.6 Hz, 2H),
2.38 (s, 6H), 2.33 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
143.8, 139.7, 137.2, 130.4, 129.6, 129.1, 126.8, 126.7, 21.8,
21.3.
Dodecyl(mesityl)sulfane (3al): Rf
= 0.9 (Hexane);
Colourless liquid; yield 86% (81 mg); 1H NMR (400 MHz,
CDCl3) δ 6.94 (s, 2H), 2.62 (t, J = 7.4 Hz, 2H), 2.52 (s,
6H), 2.27 (s, 3H), 1.62 – 1.47 (m, 2H), 1.44 – 1.30 (m, 4H),
1.29 – 1.25 (s, 14H), 0.90 (t, J = 6.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 143.0, 137.9, 130.8, 129.0, 35.7, 32.1,
30.0, 29.8 (x2), 29.7, 29.6, 29.5, 29.4, 29.1, 22.8, 22.1,
21.1, 14.3, IR (KBr) ῡ = 2924, 2853, 2729, 2058, 1631,
1462,1374, 1295, 848, 721 cm-1; HRMS (ESI-TOF) calcd
for C21H36S (M + H)+ 321.2610, found 321.2599.
(4-Fluorophenyl)(mesityl)sulfane (3ad): Rf
=
0.85
(Hexane); Colourless liquid; yield 95% (110 mg); 1H NMR
(400 MHz, DMSO) δ 7.14 – 7.08 (m, 2H), 7.07 (s, 2H),
6.95 – 6.87 (m, 2H), 2.31 (s, 6H), 2.27 (s, 3H); 13C NMR
1
(175 MHz, CDCl3) δ 160.8 (d, JCF = 243.6 Hz), 143.7,
(4-Bromophenyl)(2,4,6-trimethoxyphenyl)sulfane
(3ba):[3] Rf = 0.3 (5% ethyl acetate /hexane); White solid;
yield 63% (71 mg); mp 130 – 132 ºC; 1H NMR (400 MHz,
CDCl3) δ 7.25 (d, J = 8.6 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H),
6.21 (s, 2H), 3.87 (s, 3H), 3.80 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 163.3, 162.6, 138.3, 131.5, 127.4, 117.9,
98.3, 91.4, 56.4, 55.6.
139.5, 133.5 (d, 4JCF = 3.1 Hz), 129.6, 127.5, 127.4 (d, 3JCF
= 7.7 Hz), 116.1 (d, 2JCF = 21.9 Hz), 21.8, 21.3; IR (KBr)
ῡ = 2921, 2037, 1875, 1602, 1488, 1227, 629, 558; HRMS
(ESI-TOF) calcd for C15H15FS (M)+ 246.0873, found
246.0873.
Mesityl(p-tolyl)sulfane (3ae):[3] Rf = 0.9 (Hexane); White
solid; yield 94% (110 mg); mp 90 – 94 ºC (lit.[7b] 88 – 90
(4-Bromophenyl)(2,3,6-trimethoxyphenyl)sulfane (3ca):
Rf = 0.3 (5% ethyl acetate /hexane); off white solid; yield
74% (84 mg); mp 76 - 78 ºC; 1H NMR (400 MHz, DMSO)
δ 7.43 (d, J = 8.6 Hz, 2H), 7.01 (s, 1H), 6.93 (d, J = 8.6 Hz,
2H), 6.83 (s, 1H), 3.86 (s, 3H), 3.75 (s, 3H), 3.69 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 154.7, 151.2, 143.5, 137.5,
131.8, 128.7, 119.2, 118.9, 109.6, 98.0, 56.9, 56.6, 56.2; IR
(KBr) ῡ = 2933, 2840, 2531, 2030, 1632, 1581, 1470,
1208, 812, 737 cm-1; HRMS (ESI-TO F) calcd for
C15H15BrO3S (M)+ 353.9920, found 353.9924.
1
ºC); H NMR (400 MHz, CDCl3) δ 7.05 – 6.96 (m, 4H),
6.85 (d, J = 8.2 Hz, 2H), 2.40 (s, 6H), 2.33 (s, 3H), 2.28 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 143.8, 139.2, 134.9,
134.3, 129.8, 129.4, 127.6, 125.8, 21.9, 21.3, 21.0.
Mesityl(4-methoxyphenyl)sulfane (3af):[3] Rf = 0.8 (5%
ethyl acetate in hexane); White solid; yield 97% (122 mg);
mp 75 – 77 ºC; 1H NMR (400 MHz, CDCl3) δ 6.99 (s, 2H),
6.91 (d, J = 8.4 Hz, 2H), 6.76 (d, J = 8.4 Hz, 2H), 3.75 (s,
3H), 2.40 (s, 6H), 2.31 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 157.6, 143.5, 139.0, 129.4, 129.1, 128.5, 127.8,
114.8, 55.4, 21.9, 21.2.
(4-Bromophenyl)(4-methoxyphenyl)sulfane (3da):[43] Rf
= 0.4 (Hexane); White solid; yield 56% (52 mg); mp 72 –
1
74 ºC; H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.2 Hz,
Mesityl(4-nitrophenyl)sulfane (3ag):[3] Rf = 0.6 (5% ethyl
2H), 7.33 (d, J = 8.2 Hz, 2H), 7.00 (d, J = 8.2 Hz, 2H),
6.91 (d, J = 8.2 Hz, 2H), 3.83 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 160.3, 138.3, 135.8, 132.0, 129.6, 123.7, 119.5,
115.3, 55.5.
acetate in hexane); light yellow solid; yield 80% (85 mg);
1
mp 86 – 88 ºC (lit.[7b] 83 – 85 ºC); H NMR (400 MHz,
CDCl3) δ 8.02 (d, J = 8.8 Hz, 2H), 7.06 (s, 2H), 6.97 (d, J
= 8.8 Hz, 2H), 2.36 (s, 6H), 2.35 (s, 3H); 13C NMR (100
MHz, CDCl3) δ = 148.8, 144.9, 143.8, 140.7, 129.9, 124.9,
124.8, 124.2, 21.6, 21.3 cm-1.
(4-Methoxy-2,6-dimethylphenyl)(phenyl)sulfane
(3eb):[44] Rf = 0.8 (5% ethyl acetate /hexane); White solid;
1
yield 80% (115 mg); mp 77 – 79 ºC; H NMR (400 MHz,
Mesityl(4-(trifluoromethyl)phenyl)sulfane (3ah): Rf =
0.75 (Hexane); White solid; yield 90% (119 mg); mp 72 –
CDCl3) δ 7.20 (t, J = 7.6 Hz, 2H), 7.07 (t, J = 7.2 Hz, 1H),
6.98 – 6.90 (m, 2H), 6.79 (s, 2H), 3.84 (s, 3H), 2.44 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 160.2, 145.7, 138.9,
128.9, 125.3, 124.5, 121.5, 114.0, 55.3, 22.2.
1
74 ºC; H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 7.8 Hz,
2H), 7.05 (s, 2H), 6.98 (d, J = 7.8 Hz, 2H), 2.38 (s, 6H),
2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 143.9, 140.1,
1
129.7, 126.8, 126.5, 125.82 (q, JCF = 3.7 Hz), 125.6, 125.1, (4-(Tert-butyl)-2,6-dimethylphenyl)(phenyl)sulfane
123.1, 21.7, 21.3; IR (KBr) ῡ = 2973, 1909, 1604, 1401,
1323, 1173, 827, 589; HRMS (ESI-TOF) calcd for
C16H15F3S (M)+ 296.0841, found 296.0829.
(3fb):[45] Rf = 0.8 (Hexane); White solid; yield 90% (132
mg); mp 67 – 71 ºC; 1H NMR (400 MHz, CDCl3) δ 7.21
(s, 2H), 7.18 (d, J = 7.6 Hz, 2H), 7.06 (t, J = 7.2 Hz, 1H),
6.94 (d, J = 8.2 Hz, 2H), 2.43 (s, 6H), 1.35 (s, 9H); 13C
NMR (100 MHz, CDCl3) δ 152.5, 143.5, 138.6, 129.0,
127.2, 125.8, 125.7, 124.6, 34.6, 31.4, 22.2.
(2-Fluorophenyl)(mesityl)sulfane (3ai): Rf
=
0.8
(Hexane); Colourless liquid; yield 96% (132 mg); 1H NMR
(400 MHz, DMSO) δ 7.25 – 7.15 (m, 2H), 7.12 (s, 2H),
7.03 (t, J = 7.6 Hz, 1H), 2.30 (s, 6H), 2.29 (s, 3H); 13C
(3-Bromo-2,4,6-trimethylphenyl)(phenyl)sulfane
1
NMR (100 MHz, CDCl3) δ 159.4 (d, JCF = 243.5 Hz),
(3gb):[45] Rf = 0.85 (Hexane); White solid; yield 42% (77
mg); mp 52 – 54 ºC; 1H NMR (400 MHz, CDCl3) δ 7.19 (t,
J = 7.6 Hz, 2H), 7.11 (s, 1H), 7.07 (t, J = 7.4 Hz, 1H), 6.91
(d, J = 8.2 Hz, 2H), 2.64 (s, 3H), 2.44 (s, 3H), 2.37 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 143.5, 142.7, 139.9, 137.9,
130.5, 129.4, 129.1, 126.0, 125.8, 125.0, 24.4, 23.2, 21.9.
144.1, 139.7, 129.6, 126.7 (d, 4JCF = 2.6 Hz), 125.9 (d, 3JCF
= 7.4 Hz), 125.7 (d, 2JCF = 16.9 Hz), 125.2, 124.6 (d, 3JCF
=
2
3.4 Hz), 115.3 (d, JCF = 21.1 Hz), 21.7, 21.3; IR (KBr) ῡ
2950, 2724, 1998, 1601, 1469, 1217, 849, 748 cm-1;
HRMS (ESI-TOF) calcd for C15H15FS (M + H)+ 247.0951,
found 247.0951.
4,6-dimethoxy-2-methyl-3-(phenylthio)benzaldehyde
(3lb): Rf = 0.1 (10% ethyl acetate /hexane); White solid;
yield 90% (154 mg); mp 145 - 150 ºC; 1H NMR (400 MHz,
CDCl3) δ 10.53 (s, 1H), 7.17 (t, J = 7.6 Hz, 2H), 7.06 (t, J
(3-Chlorophenyl)(mesityl)sulfane (3aj): Rf
=
0.85
(Hexane); Colourless liquid; yield 96% (130 mg); 1H NMR
(400 MHz, CDCl3) δ 7.09 (t, J = 7.8 Hz, 1H), 7.05 – 7.00
(m, 3H), 6.87 (s, 1H), 6.79 (d, J = 7.8 Hz, 1H), 2.38 (s, 6H), = 7.4 Hz, 1H), 6.96 (d, J = 7.6 Hz, 2H), 6.44 (s, 1H), 3.98
2.33 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 143.9, 140.9,
139.9, 135.0, 130.0, 129.7, 126.1, 125.1, 124.8, 123.6, 21.8,
21.3; IR (KBr) ῡ = 2843, 2077, 1639, 1575, 1459, 1256,
850, 773 cm-1; HRMS (ESI-TOF) calcd for C15H15ClS
(M)+ 262.0578, found 262.0572.
(s, 3H), 3.89 (s, 3H), 2.77 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 190.7, 166.1, 165.7, 149.8, 137.9, 128.9, 125.9,
124.9, 118.3, 113.1, 92.9, 56.5, 56.0, 18.7; IR (KBr) ῡ =
2981, 2072, 1653, 1574, 1467, 1317, 1213, 815, 743 cm-1;
HRMS (ESI-TOF) calcd for C16H16O3S (M + H)+ 289.0893,
found 289.0917.
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801510
Advanced Synthesis & Catalysis
1-((4-Methoxyphenyl)sulfinyl)-2,4-dimethylbenzene
(2,5-Dimethoxy-1,4-phenylene)bis(phenylsulfane)
(3ib):[14d] Rf = 0.5 (5% ethyl acetate /hexane); White solid;
yield 74% (77 mg); mp 148 - 150 ºC; 1H NMR (400 MHz,
CDCl3) δ 7.39 – 7.35 (m, 1H), 7.35 – 7.33 (m, 4H), 7.33 –
7.31 (m, 2H), 7.31 – 7.27 (m, 2H), 7.26 – 7.24 (m, 1H),
6.65 (s, 2H), 3.65 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
152.0, 134.4, 131.5, 129.4, 127.4, 123.9, 114.7, 56.6.
(4hf): Rf = 0.2 (20% Ethyl acetate in hexane); Colourless
1
liquid; yield 50% (60 mg); H NMR (400 MHz, CDCl3) δ
7.86 (d, J = 8.0 Hz, 1H), 7.55 – 7.47 (m, 2H), 7.22 (d, J =
8.2 Hz, 1H), 6.97 (s, 1H), 6.95 – 6.90 (m, 2H), 3.80 (s, 3H),
2.34 (s, 3H), 2.22 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
161.9, 141.2, 139.8, 136.0, 135.4, 131.8, 128.3, 127.8,
124.6, 114.8, 55.6, 21.4, 18.5; IR (KBr) ῡ = 2837, 2046,
1636, 1591, 1490, 1253, 827, 615 cm-1; HRMS (ESI-TOF)
calcd for C15H16O2S (M + H)+ 261.0944, found 261.0964.
(4-Methoxyphenyl)(p-tolyl)sulfane (3de):[46] Rf = 0.85
(Hexane); White solid; yield 52% (76 mg); mp 48 – 50 ºC
(lit.[47] 46 – 48 ºC); 1H NMR (400 MHz, CDCl3) δ 7.38 (d,
J = 8.4 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0
Hz, 2H), 6.88 (d, J = 8.4 Hz, 2H), 3.82 (s, 3H), 2.32 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 159.6, 136.2, 134.4
(x2), 129.9, 129.5, 125.8, 115.0, 55.5, 21.1.
1,3,5-Trimethoxy-2-(phenylsulfinyl)benzene (4bb): Rf =
0.2 (50% ethyl acetate/hexane); White solid; yield 44% (76
1
mg); mp 114 – 116 ºC; H NMR (400 MHz, DMSO) δ
7.50 – 7.35 (m, 5H), 6.26 (s, 2H), 3.81 (s, 3H), 3.66 (s,
6H); 13C NMR (100 MHz, DMSO) δ 164.82, 160.8, 145.6,
129.1, 128.4, 123.8, 112.2, 91.7, 56.1, 55.7; IR (KBr) ῡ =
3007, 2842, 2074, 1592, 1413, 1229, 750, 698 cm-1;
HRMS (ESI-TOF) calcd for C15H16O4S (M + H)+ 293.0842,
found 293.0812.
(2,4-Dimethylphenyl)(4-methoxyphenyl)sulfane
(3hf):[48] Rf = 0.8 (5% Ethyl acetate in hexane); Colourless
1
liquid; yield 44% (53 mg); mp ºC; H NMR (400 MHz,
CDCl3) δ 7.29 – 7.23 (m, 2H), 7.07 – 6.98 (m, 2H), 6.91 (d,
J = 8.0 Hz, 1H), 6.86 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H),
2.35 (s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
159.2, 138.3, 136.9, 133.3, 132.7, 131.4, 131.0, 127.4,
126.0, 115.0, 55.5, 21.1, 20.5.
5-(tert-butyl)-1,3-dimethyl-2-(phenylsulfinyl)benzene
(4fb): Rf = 0.3 (5% ethyl acetate /hexane); White solid;
yield 77% (130 mg); mp 119 – 121 ºC; 1H NMR (400 MHz,
CDCl3) δ 7.48 – 7.34 (m, 5H), 7.04 (s, 2H), 2.45 (s, 6H),
1.28 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 155.2, 144.4,
139.7, 136.6, 129.5, 128.9, 127.3, 124.7, 34.7, 31.1, 19.8;
IR (KBr) ῡ = 2962, 2868, 2072, 1633, 1592, 1442, 1362,
1227, 749, 695 cm-1; HRMS (ESI-TOF) calcd for
2-((4-Bromophenyl)sulfinyl)-1,3,5-trimethylbenzene
(4aa): Rf = 0.2 (5% ethyl acetate /hexane); White solid;
yield 94% (96 mg); mp 120 – 122 ºC; 1H NMR (400 MHz,
CDCl3) δ 7.55 (d, J = 8.6 Hz, 2H), 7.29 (d, J = 8.6 Hz, 2H), C18H22OS (M + H)+ 287.1464, found 287.1471.
6.87 (s, 2H), 2.41 (s, 6H), 2.29 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 143.8, 142.6, 140.0, 136.3, 132.1, 131.0,
126.4, 124.1, 21.3, 19.5; IR (KBr) ῡ = 2855, 2069, 1635,
1463, 1382, 1239,811, 722 cm-1; HRMS (ESI-TOF) calcd
for C15H15BrOS (M + H)+ 323.0100, found 323.0102.
1,3,5-Triethyl-2-(phenylsulfinyl)benzene (4jb): Rf = 0.15
(5% ethyl acetate /hexane); Colourless liquid; yield 80%
1
(135 mg); H NMR (400 MHz, CDCl3) δ 7.45 – 7.32 (m,
5H), 6.96 (s, 2H), 2.97 – 2.74 (m, 4H), 2.62 (q, J = 7.6 Hz,
2H), 1.23 (t, J = 7.6 Hz, 3H), 1.05 (t, J = 7.2 Hz, 6H); 13C
NMR (100 MHz, CDCl3) δ 148.9, 146.7, 145.8, 136.3,
129.4, 128.9, 128.1, 124.8, 28.8, 25.6, 16.1, 15.2; IR (KBr)
ῡ = 2966, 2932, 2872, 2724, 1596, 1442, 1374, 1173, 744,
695 cm-1; HRMS (ESI-TOF) calcd for C18H22OS (M + H)+
287.1464, found 287.1467.
1,3,5-Trimethyl-2-(phenylsulfinyl)benzene (4ab): Rf =
0.25 (5% Ethyl acetate in hexane); Colourless liquid; yield
1
82% (118 mg); H NMR (400 MHz, CDCl3) δ 7.45 – 7.31
(m, 5H), 6.85 (s, 2H), 2.40 (s, 6H), 2.26 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 144.4, 142.2, 139.9, 136.6, 130.8,
129.5, 128.8, 124.5, 21.2, 19.4; IR (KBr) ῡ = 3055, 2923,
2403, 1600, 1442, 1294, 748, 694; HRMS (ESI-TOF)
calcd for C15H16OS (M + H)+ 245.0995, found 245.0997.
1-methoxy-4-(phenylsulfinyl)benzene (4db):[49] Rf = 0.2
(20% ethyl acetate /hexane); Colourless liquid; yield 82%
1
(110 mg); H NMR (400 MHz, CDCl3) δ 8.12 – 7.78 (m,
2-((4-Methoxyphenyl)sulfinyl)-1,3,5-trimethylbenzene
4H), 7.67 – 7.37 (m, 3H), 6.96 (d, J = 8.8 Hz, 2H), 3.84 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 162.0, 145.8, 136.7,
130.7, 129.2, 127.2, 124.5, 114.8, 55.4.
(4af): Rf = 0.15 (5% Ethyl acetate in hexane); off white
1
solid; yield 81% (109 mg); mp 95 – 97 ºC; H NMR (400
MHz, CDCl3) δ 7.33 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8
Hz, 2H), 6.86 (s, 2H), 3.82 (s, 3H), 2.42 (s, 6H), 2.28 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 160.9, 142.1, 140.0,
136.7, 135.5, 130.9, 126.3, 114.5, 55.6, 21.3, 19.4; IR
(KBr) ῡ = 2959, 2837, 2550, 2046, 1594, 1492, 1250,
1172, 828, 794 cm-1; HRMS (ESI-TOF) calcd for
C16H18O2S (M + H)+ 275.1100, found 275.1120.
1-Methyl-3-phenoxy-2-(phenylsulfinyl)benzene (4kb):
Rf = 0.15 (5% Ethyl acetate in hexane); Colourless liquid;
1
yield 86% (156 mg); H NMR (400 MHz, CDCl3) δ 7.80
(d, J = 8.6 Hz, 1H), 7.65 – 7.56 (m, 2H), 7.50 – 7.41 (m,
3H), 7.36 (t, J = 7.8 Hz, 2H), 7.16 (t, J = 7.6 Hz, 1H), 7.02
(d, J = 7.8 Hz, 2H), 6.94 (dd, J = 8.68; 2.2 Hz, 1H), 6.78 (d,
J = 2.2 Hz, 1H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 160.2, 155.8, 144.9, 138.5, 136.8, 131.0, 130.1, 129.4,
127.4, 125.6, 124.4, 120.1, 120.0, 116.5, 18.8; IR (KBr) ῡ
= 2966, 2880, 1585, 1472, 1232, 744, 695 cm-1; HRMS
(ESI-TOF) calcd for C19H16O2S (M + H)+ 309.0944, found
309.0956.
1,3,5-trimethyl-2-((4-
(trifluoromethyl)phenyl)sulfinyl)benzene (4ah): Rf
=
0.15 (5% Ethyl acetate in hexane); White solid; yield 52%
(72 mg); mp 108 - 110 ºC; H NMR (400 MHz, CDCl3) δ
1
7.68 (d, J = 8.2 Hz, 2H), 7.56 (d, J = 8.2 Hz, 2H), 6.89 (s,
2H), 2.41 (s, 6H), 2.30 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 149.2, 142.9, 140.1, 136.2, 131.9, 131.6, 131.1,
125.9 (q, J = 3.7 Hz), 125.2, 21.3, 19.5; IR (KBr) ῡ =
2894, 2070, 1635, 1398, 1321, 1127, 826, 695 cm-1;
HRMS (ESI-TOF) calcd for C16H15F3OS (M + H)+
313.0868, found 313.0892.
2-(Dodecylsulfinyl)-1,3,5-trimethylbenzene (4al):[50] Rf =
0.25 (5% ethyl acetate /hexane); Colourless liquid; yield
1
66% (56 mg); H NMR (400 MHz, CDCl3) δ 6.85 (s, 2H),
3.29 – 3.19 (m, 1H), 2.85 – 2.76 (m, 1H), 2.53 (s, 6H),
2.28 (s, 3H), 1.85 – 1.71 (m, 1H), 1.70 – 1.61 (m, 2H),
1.51 – 1.38 (m, 2H), 1.35 – 1.26 (m, 5H), 1.25 – 1.23 (s,
10H), 0.87 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 141.1, 138.5, 135.2, 131.0, 52.6, 32.0, 29.7, 29.7
2-((3-Chlorophenyl)sulfinyl)-1,3,5-trimethylbenzene
(4aj): Rf = 0.2 (5% Ethyl acetate in hexane); White solid;
yield 90% (130 mg); mp 112 – 114 ºC; 1H NMR (400 MHz, (x2), 29.5, 29.4, 29.3, 28.9, 23.9, 22.8, 21.2, 19.4, 14.3.
CDCl3) δ 7.43 (s, 1H), 7.38 – 7.33 (m, 2H), 7.31 – 7.25 (m,
1H), 6.89 (s, 2H), 2.42 (s, 6H), 2.30 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 146.8, 142.7, 140.1, 136.1, 135.3,
131.1, 130.2, 129.9, 124.8, 122.9, 21.3, 19.5; IR (KBr) ῡ
2922, 2851, 2728, 1600, 1573, 1457, 1294, 1076, 784, 680
cm-1; HRMS (ESI-TOF) calcd for C15H15ClOS (M + H)+
279.0605, found 279.0602.
3-(phenylthio)-1H-indole (3mb):[51] Rf = 0.35 (5% ethyl
acetate /hexane); off white solid; mp 155-157 ºC; yield
1
41% (54 mg); H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H),
7.62 (d, J = 8.0 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 7.45 (d,
J = 8.0 Hz, 1H), 7.30 – 7.26 (m, 1H), 7.20 – 7.14 (m, 3H),
7.13 – 7.09 (m, 2H), 7.05 (t, J = 7.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 139.4, 136.6, 130.8, 129.3, 128.8,
126.0, 124.9, 123.2, 121.0, 119.8, 111.7, 103.0.
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801510
Advanced Synthesis & Catalysis
d) C. J. Nalbandian, Z. E. Brown, E. Alvarez, J. L.
Gustafson, Org. Lett. 2018, 20, 3211-3214.
[14] a) P. Wang, S. Tang, P. Huang, A. Lei, Angew. Chem.
Int. Ed. 2017, 56, 3009-3013; b) S. K. R. Parumala, R.
K. Peddinti, Green Chem. 2015, 17, 4068-4072; c) Z.
Huang, D. Zhang, X. Qi, Z. Yan, M. Wang, H. Yan, A.
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Acknowledgements
We thank Dr. Arindam Ghosh (NISER) for crystallography. K.C.
and S.M. thank NISER and CSIR (India) for fellowship,
respectively.
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Iodine(III) Enabled Dehydrogenative Aryl C-S
Coupling by in situ Generated Sulfenium Ion
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Khokan Choudhuri, Saikat Maiti and Prasenjit
Mal*
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