Palladium-catalyzed three-component cascade arylthiolation with aryldiazonium salts asS-arylation sources

Article abstract of DOI:10.1039/d0ob00828a

A novel and efficient palladium-catalyzed three-component cascade cyclization/arylthiolation has been developed for the assembly of diverse 3-sulfenylindole and 3-sulfenylbenzofuran derivatives from 2-alkynylamines and 2-alkynylphenols, aryldiazonium salts, and Na₂S₂O₃under aerobic conditions with PEG-200 as an environmentally benign medium. The current study features exceptional functional group tolerance without additional ligands, oxidants or silver salts, and eco-friendly mild reaction conditions. The ionic liquid [C₂OHmim]Cl plays a crucial role in this protocol as an environmentally friendly additive. Notably, this procedure represents the first example of the use of aryldiazonium salts as directS-arylation sources in this type of chemical transformation.

Full text of DOI:10.1039/d0ob00828a

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DOI: 10.1039/D0OB00828A
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Palladium-catalyzed three-component cascade arylthiolation with
aryldiazonium salts as S-arylation sources
Jianxiao Li,*,a, b Hao Tang, a Zidong Lin,a Shaorong Yang,a Wanqing Wua and Huanfeng Jiang*,a
Received 00th January 20xx,
Accepted 00th January 20xx
A novel and efficient palladium-catalyzed three-component cascade cyclization/arylthiolation for the assembly of diverse
3-sulfenylindoles and 3-sulfenylbenzofurans derivatives from 2-alkynylamines and 2-alkynylphenols, aryldiazonium salts,
and Na2S2O3 under aerobic conditions with PEG-200 as an environmentally benign medium has been developed. The
current study features exceptional functional group tolerance, without additional ligand or oxidant or silver salt, eco-
friendly, and mild reaction conditions. Ionic liquids [C2OHmim]Cl as the environmental friendliness additive plays crucial
roles in this protocol. Notably, this procedure represents the first example for the use of aryldiazonium salts as the direct
S-arylation sources in this type chemical transformation.
DOI: 10.1039/x0xx00000x
www.rsc.org/
arylhydrazines, and organosilicon reagents as the aryl sources.
Nevertheless, the direct cascade S-arylation reagents have
remained relatively rare. Therefore, it is highly desirable to explore
new type S-arylation reagents and catalytic system for the direct S-
arylation reaction under eco-friendly conditions.
Introduction
Organosulfur heterocyclic scaffolds are considered as versatile and
important privileged architecture in numerous pharmaceuticals,
advanced materials, and biologically active molecules because of
these building blocks have unique versatility and availability.[1] In
this regard, transition-metal-catalyzed sulfenylation reaction have
witnessed considerable attention in the recent years, which can
effective assemble structurally diverse sulfur-containing
frameworks in a rather straightforward, atom- and step-economical
manners.[2] Correspondingly, a number of sulfenylating agents, such
as thiols, disulfides, arylsulfonyl chlorides, sulfonyl hydrazides, and
N-thioarylphthalimides, have been investigated as the sulfur
sources. However, all of these elegant developments suffer from
certain limitations such as repulsive odor, air or water sensitivity,
instability and toxic. As the another green, and highly efficient
sulfenylation process, transition metal-free synthetic methods for
the preparation of high value-added sulfur-containing structural
motifs have also been well established.[3] Alternative inorganic
sulfenylating reagents such as S8, Na2S, K2S, sodium sulfinates,
sodium thiosulfate, and sulfourea, have also been exploited in
recent years. Particularly, a wide array of cascade S-arylation
reaction for the rapid synthesis of structural complexity. Jiang,[4]
Willis,[5] Wu,[6] Deng,[7] Tang,[8] and our group[9] have established a
number of cascade S-arylation methodologies for the construction
of unconventional and more elaborated heterocyclic organosulfur
frameworks by employing aryl halides, arylboronic acid,
In addition, as one of important heterocyclic building blocks,
highly substituted indoles derivatives exhibit remarkable biological
activities and pharmaceuticals activities.[10] It is worth noting that 3-
sulfenylindoles display a broad spectrum of biological activities,
which can be employed as the drugs assessed for the treatment of
heart diseases, bacterial infection, obesity, and cancer diseases.[11]
As a result, a wide array of outstanding methodologies have been
studied for the construction of these organosulfur heterocyclic
frameworks. Generically, there are three representative methods
are typically employed in this field. Transition-metal-catalyzed
sulfenylation of indoles with various sulfurating reagents have been
identified as the most efficient and direct synthetic approach for
constructing these heterocyclic scaffolds (Scheme 1a).[12] For
instance, Yuan and co-workers developed a novel approach for the
synthesis of 3-sulfenylindoles via cobalt-catalyzed aerobic cross-
dehydrogenative coupling in water with thiols as the sulfenylating
agents.[12d] Moreover, metal free procedure for the direct assembly
of 3-sulfenylindoles from indoles with sulfurating reagents have
also been developed.[13] For example, Iida and co-workers
performed a novel organocatalyst systems flavin-iodine-catalysed
sulfenylation of indoles with thiols under mild conditions.[13e] On
the other hand, transition-metal-catalyzed cascade electrophilic
annulation/arylthiolation reaction using 2-alkynylanilines as the
readily accessible starting materials to prepare structurally diverse
3-sulfenylindoles derivatives (Scheme 1b).[14] Using this strategy, Li
and Zhang described a metal-involved annulations approach from
2-(1-alkynyl)benzenamines and disulfides.[14b] Especially, our group
also demonstrated an unprecedented palladium-catalyzed cascade
annulation/arylthiolation reaction the rapid assembly of 3-
sulfenylindole derivatives from readily available 2-alkynylamines in
a
Key Laboratory of Functional Molecular Engineering of Guangdong Province,
School of Chemistry and Chemical Engineering, South China University of
Technology, Guangzhou 510640 (P. R. China), E-mail: cewuwq@scut.edu.cn;
jianghf@scut.edu.cn
b
Guangdong Provincial Key Laboratory of Luminescence from Molecular
Aggregates, South China University of Technology, Guangzhou 510640, China
†Electronic Supplementary Information (ESI) available: General experimental
information, and NMR spectra. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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ionic liquids with elemental sulfur as the ideal sulfur sources.[9a] yield (Entry 15). However, the yield decreased dramatically when
View Article Online
o
DOI: 10.1039/D0OB00828A
Recently, our group have also successfully discovered an elegant the temperature was used at 80 C under the similar condition
palladium-catalyzed three-component cascade S-transfer reaction (Entry 14). Gratifyingly, when the reaction was performed with 1
of acetylinic oximes with aryl halides using readily available Na2S2O3 mol% dosage of the Pd-3 catalyst, the desired product 3a was still
as an odorless sulfenylation reagent under aerobic conditions in obtained in 89% GC yield (Entry 16). Finally, in the absence of any
ionic liquids for the assembly of 4-sulfenylisoxazole derivatives.[15] palladium catalysts, neither of the starting materials were
To our knowledge, there are no examples disclosed the direct consumed (Entry 17).
arylation of indoles using aryldiazonium salts as the S-aryl sources.
Inspired by our previous studies for the synthesis of organosulfur
Table 1. Optimization of reaction conditions.a
frameworks,[16] and our longstanding interest in Pd-catalyzed cross-
coupling reactions of alkynes,[17] herein we describe an efficient and
novel palladium-catalyzed three-component cascade S-arylation
reaction for the assembly of structurally diverse 3-sulfenylindoles
and 3-sulfenylbenzofurans derivatives from 2-alkynylamines and 2-
alkynylphenols, aryldiazonium salts, and Na2S2O3 under aerobic
conditions with PEG-200 as an environmentally benign medium
(Scheme 1c).
Entry
1
Catalyst
Pd(OAc)2
PdCl2
Additive
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NBr
nBu4NI
Solvent
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Yield (%)b
0
2
trace
11
3
Pd(PhCN)2Cl2
[Pd(allyl)Cl]2
Pd-1
4
34
5
28
6
Pd-2
45
7
Pd-3
57
8
Pd-4
35
9
Pd-3
40
10
11
12
13
14c
15d
16e
17
Pd-3
[Bmim]Cl
[C2OHmim]Cl
50
Pd-3
68
Pd-3
[C2OHmim]Cl Toluene
26
Pd-3
[C2OHmim]Cl
[C2OHmim]Cl
[C2OHmim]Cl
[C2OHmim]Cl
[C2OHmim]Cl
PEG-
PEG-
PEG-
PEG-
PEG-
89 (82)
67
Pd-3
Pd-3
89
Pd-3
89
Scheme 1 Representative strategies for the synthesis of 3-sulfenylindoles
-
0
a
Reactions were performed with 1a (0.10 mmol), 2a (0.12 mmol), Na2S2O3 (0.20
Results and discussion
mmol), catalyst (2 mol %), additives (0.20 mmol), solvent (1 mL) at 100 oC under
b
air for 16 h; Determined by GC using dodecane as the internal standard. The
We
commenced
our
investigation
by
choosing
2-
c
d
e
value in parentheses is the yield of isolated product. At 80 oC; At 110 oC.
1
(phenylethynyl)aniline (1a), phenyldiazonium salts (2a), and sodium
thiosulfate (Na2S2O3) as the model substrates to optimize the
reaction conditions, and the representative results are summarized
in Table 1.[18] Initially, no the desired product 3a was detected in the
presence of conventional palladium catalysts such as Pd(OAc)2 and
PdCl2 in DMF at 100 °C for 16 h (Entries 1-2). Further investigation
on the complex palladium catalysts showed that Pd-3 was the
optimal catalyst for this chemical transformation, and the desired
3a could be detected in 57% GC yield (Entry 7). In light of our
previously observed results, we found that ionic liquids as the
mol% Pd-3 was used.
With the optimized conditions in hand, we then explored the
substrate scope of various 2-alkynylamines, and the representative
results are presented in Table 2. As anticipated, both electron-
donating and electron-withdrawing substituents on the phenyl ring
were perfectly accommodated with the current catalytic system,
furnishing the corresponding 3-sulfenylindole derivatives in
moderate to good yields. It is worth mentioning that substrates
bearing electron-donating groups can give better yields than the
ones with electron-withdrawing groups. Specifically, various
additive showed apparent positive effects for the cascade
[17b]
annulation process.
Various ionic liquids additives were next
tested, and the ionic liquid [C2OHmim]Cl was superior to the others
under the same conditions (Entry 11). Subsequently, different type
solvents were also estimated such as DMSO, Toluene, PEG-200, and
PEG-400, it was revealed that PEG-200 was found to be the best
choice (Entry 13). In addition, when the reaction was performed at
110 oC for 16 h, the desired product 3a was still obtained in 89% GC
2 | J. Name., 2012, 00, 1-3
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halogen atom such as F, Cl, and Br group were compatible with this
chemical transformation, giving the corresponding products 3c, 3d,
and 3e in 66%, 72%, and 70% yields, respectively. Moreover, the
obtained products can allow for further synthetic transformations
by transition metal-catalyzed cross-coupling reactions. Delightfully,
strong electron-withdrawing group such as CF3 group on the
benzene ring was well tolerated, producing the desired product 3f
in 53% yield. Additionally, the 2-thienyl and 2-vinyl group were
amenable to this transformation, and offered the corresponding
products 3j and 3k in 70% and 71% yields, respectively. Notably,
amino substituted 2-alkynylamine 1l was also perfectly tolerated,
and gave the desired 3l in 60% yield. Substrates bearing hydroxyl
group was compatible with the current protocol, however, only a
messy mixture 3o was obtained.
View Article Online
DOI: 10.1039/D0OB00828A
a
Reaction conditions: 4 (0.20 mmol), 2 (0.24 mmol), Na2S2O3 (0.40 mmol), Pd-3 (1
mol %), [C2OHmim]Cl (0.4 mmol), PEG-200 (1 mL) at 100 oC under air for 16 h; Yields
referred to isolated yield.
Table 2. Substrate scope of various 2-alkynylamines a
Furthermore, we turned our attention to the different sulfur
sources under the standard reaction conditions. As illustrated in
Table 4, other easily available inorganic sulfur sources such as Na2S,
S8, and Na2S2O5 were not compatible with the current protocol, and
failed to offer the desired product 3a. In contrast, when PhSH was
employed as a sulfenylating agents, the desired product 3a was
detected in 26% GC yield. Unfortunately, no desired product 3a was
observed when PhSSPh was applied as the sulfenylating agent.
Table 4. Investigation of different sulfur sources
[S] Source
GC yields
Na2S
-
PhSH
26%
S8
-
PhSSPh
-
Na2S2O5
-
a
Subsequently, a gram-scale synthesis of 3a was performed under
the optimized reaction conditions (Scheme 2). When 3 mmol of 1a
was utilized, 0.651 g of the desired product 3a was obtained in 72%
yield. Notably, when 5 mmol of 1a was explored, the product 3a
was also generated in 68% yield.
Reaction conditions: 1 (0.20 mmol), 2a (0.24 mmol), Na2S2O3 (0.40 mmol), Pd-3 (1
mol %), [C2OHmim]Cl (0.4 mmol), PEG-200 (1 mL) at 100 oC under air for 16 h; Yields
referred to isolated yield.
Encouraged by the above sulfenylation results, we next
investigated the scope of various structurally diverse 2-
alkynylphenols and different diazonium salts under the optimal
conditions, and the experimental results are illustrated in Table 3.
Various 2-alkynylphenols with electron-donating substituents (tBu,
OMe) and electron-withdrawing groups (Cl, Br, CO2Me, NO2) on the
benzene ring, reacted with phenyldiazonium salts (2a) facilely to
produce the desired products 5a-5f in 56%-84% yields. As for aryl
diazonium salts, substituents on the benzene ring such as -Me, -
OMe, -F, -Cl, and -NO2 groups were also well accommodated,
providing the expected sulfenylation products 5g, 5h, 5i, 5j, and 5k
in 80%, 90%, 75%, 76%, and 60% yields, respectively.
Scheme 2 Scale-up experiment
Satisfied with the obtained results, various aryl reagents were
then observed under the standard conditions. For instance, the
cascade Suzuki-type/annulation/arylthiolation cross-coupling of
phenylboric acid (6a), 2-(phenylethynyl)aniline (1a), and Na2S2O3
proceeded smoothly to give the product 3a in 75% yield (Scheme
3a). Similarly, the desulfitative coupling of 6b occurred uneventfully
as well, thus providing the target product 3a in 77% yield (Scheme
Table 3. Substrate scope of various 2-alkynylphenols and different diazonium
salts a
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3b). Particularly noteworthy was that the desulfitative- Subsequently, the sequential release of SO3 and the reductive
View Article Online
[19]
denitrogenative arylation cascade approach of arylsulfonyl elimination process generates the desired products.
DOI: 10.1039/DF0iOnBa0ll0y8, 2th8Ae
hydrazides 6c allowed successfully to produce the desired 3a in 56% palladium(0) species is additionally oxidized to the palladium(II)
yield (Scheme 3c).
active catalyst by air to complete this catalytic cycle.[20]
Scheme 3 Investigation of different aryl sources
Scheme 5. Possible Mechanism
To gain preliminary insights into this cascade sulfenylation
pathway, several control experiments were further conducted
(Scheme 4). First, only a trace amount of the desired product 3a
was observed when this cascade three-component tandem
cyclization reaction was performed under an N2 atmosphere
(Scheme 4a). Thus, this control reaction suggests that an aerobic
oxidative condition was irreplaceable for this chemical process.
Subsequently, when treated with 2-phenyl-1H-indole (7) and 3-
chloro-2-phenyl-1H-indole (8) with phenyl diazonium salts (2a), and
Na2S2O3 under the standard conditions, no desired product 3a was
detected by GC-MS analysis (Scheme 4b and 4c). This observation
suggested that 2-phenyl-1H-indole (7) and 3-chloro-2-phenyl-1H-
indole (8) are not possible intermediates in this cascade
sulfenylation procotol.
Conclusions
In summary, we have successfully demonstrated a novel and
efficient
palladium-catalyzed
three-component
cascade
cyclization/arylthiolation for the assembly of diverse 3-
sulfenylindoles and 3-sulfenylbenzofurans derivatives in moderate
to good yields from readily available 2-alkynylamines and 2-
alkynylphenols under aerobic conditions. This procedure represents
the first example for the use of aryldiazonium salts as a unique aryl
source in this type chemical transformation. Prominently, the ionic
liquids [C2OHmim]Cl as the optimal additive makes this
transformation green and high efficiency. Notably, the current
study demonstrates exceptional functional group tolerance, ligands
free, no additional oxidant or silver salt, eco-friendly, and operation
simplicity.
Experimental section
Materials and methods
Melting points were measured using a melting point instrument
1
and are uncorrected. H and 13C NMR spectra were recorded on a
400 MHz NMR spectrometer. The chemical shifts are referenced to
signals at 7.24 and 77.0 ppm, respectively, and chloroform was used
as a solvent with TMS as the internal standard. GC-MS data were
obtained using electron ionization. HRMS was carried out on a high-
resolution mass spectrometer (LCMS-IT-TOF). TLC was performed
using commercially available 100−400 mesh silica gel plates (GF254).
Unless otherwise noted, purchased chemicals were used without
further purification.
Scheme 4 Control experiments for mechanism study
Based on the current experiment results and previous literature
precedents, the postulated mechanism is illustrated in Scheme 5.
Initially, nucleopalladation of 2-alkynylphenols or 2-alkynylamines
gives vinyl palladium intermediate I.[17c] Meanwhile, in the presence
of palladium catalyst, aryl diazonium salts reacted with thiosulfate
affords thiosulfate complex II along with releasing nitrogen gas.
Then, ligand exchange between intermediate I and thiosulfate
intermediate II affords palladium thiosulfate intermediate III.[19]
Typical procedure for the preparation of 3-sulfenylindoles and 3-
sulfenylbenzofurans
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A 15 mL vial was charged with 2-alkynylamines or 2-alkynylphenols 128.9, 128.8, 128.2, 126.4, 125.6, 124.9, 122.5, 114.V7ie,w1A1r2tic.7le,O9n9lin.3e
+
DOI: 10.1039/D0OB00828A
1 (0.20 mmol), aryldiazonium salts 2 (0.24 mmol), Na2S2O3 (0.40 ppm; HRMS-ESI (m/z): calcd for C20H14BrNNaS, [M+Na] : 401.9923,
mmol), Pd catalyst Pd-3 (1.0 mol %), [C2OHmim]Cl (2 equiv), and found 401.9928.
PEG-200 (2 mL). After being heated at 100 oC under air for 16 h, the
[9a]
2-Phenyl-3-(phenylthio)-5-(trifluoromethyl)-1H-indole (3g).
reaction was quenched by water and extracted with CH2Cl2 three
times. The combined organic layers were dried over anhydrous
Na2SO4 and evaporated under vacuum. The residue was purified by
flash column chromatography on silica gel (hexanes/ethyl acetate)
to afford the desired products 3 or 5.
1
Yield: 53%; H NMR (400 MHz, CDCl3) δ 8.73 (s, 1H), 7.95 (s, 1H),
7.74 (d, J = 7.2 Hz, 2H), 7.48 (s, 2H), 7.46 - 7.34 (m, 3H), 7.15 (t, J =
7.2 Hz, 2H), 7.11 - 7.00 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 143.8,
138.5, 137.2, 130.9, 130.6, 129.2, 129.0, 128.8, 128.2, 125.6 (q, J =
256.4 Hz), 125.0, 123.4 (q, J = 41.8 Hz), 120.2 (q, J = 3.5 Hz), 111.6 (q,
2-Phenyl-3-(phenylthio)-1H-indole (3a).[14a] Yield: 82%; 1H NMR
(400 MHz, CDCl3) δ 8.48 (s, 1H), 7.73 (d, J = 7.6 Hz, 2H), 7.64 (d, J = C21H14F3NNaS, [M+Na]+: 392.0691, found 392.0695.
7.6 Hz, 1H), 7.36 (dt, J = 21.2, 6.8 Hz, 4H), 7.25 (t, J = 7.6 Hz, 1H),
7.12 (dt, J = 15.6, 7.2 Hz, 5H), 7.02 (t, J = 6.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 142.2, 139.4, 135.9, 131.4, 131.2, 128.9, 128.8, 128.6,
128.2, 125.6, 124.6, 123.4, 121.2, 120.0, 111.2, 99.4 ppm; HRMS-ESI
(m/z): calcd for C20H15NNaS, [M+Na]+: 324.0817, found 324.0823.
J = 4.2 Hz), 111.6, 100.7 ppm; HRMS-ESI (m/z): calcd for
2-Cyclopropyl-3-(phenylthio)-1H-indole (3h).[12c] Yield: 85%; 1H
NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.54 (d, J = 7.6 Hz, 1H), 7.27 (d,
J = 7.6 Hz, 1H), 7.18 - 7.08 (m, 6H), 7.02 (t, J = 6.8 Hz, 1H), 2.41 -
2.27 (m, 1H), 1.02 (d, J = 7.6 Hz, 2H), 0.84 (d, J = 4.8 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 146.0, 139.7, 135.0, 130.7, 128.6, 125.6,
1-Methyl-2-phenyl-3-(phenylthio)-1H-indole (3b).[9a] Yield: 86%; 124.6, 122.2, 120.7, 118.6, 110.8, 99.4, 8.3, 7.9 ppm; HRMS-ESI
1H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 8.0 Hz, 1H), 7.44 - 7.36 (m, (m/z): calcd for C17H15NNaS, [M+Na]+: 288.0817, found 288.0820.
6H), 7.30 (t, J = 7.6 Hz, 1H), 7.22 - 7.15 (m, 1H), 7.11 (t, J = 7.6 Hz,
1
3-(Phenylthio)-2-propyl-1H-indole (3i).[9a] Yield: 90%; H NMR (400
MHz, CDCl3) δ 8.17 (s, 1H), 7.55 (d, J = 7.6 Hz, 1H), 7.35 (d, J = 8.0 Hz,
1H), 7.20 (d, J = 8.6 Hz, 1H), 7.16 - 7.08 (m, 3H), 7.08 - 6.99 (m, 3H),
2.86 (t, J = 7.2 Hz, 2H), 1.79 - 1.54 (m, 2H), 0.93 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 145.4, 139.5, 135.5, 130.3, 128.8, 125.4,
124.6, 122.2, 120.7, 119.1, 110.8, 99.1, 28.6, 23.0, 14.0 ppm; HRMS-
2H), 7.04 (d, J = 7.6 Hz, 2H), 6.96 (t, J = 7.2 Hz, 1H), 3.68 (s, 3H); 13
C
NMR (100 MHz, CDCl3) δ 145.8, 140.1, 137.6, 130.7, 130.6, 129.8,
128.8, 128.7, 128.4, 125.6, 124.5, 122.8, 121.1, 119.8, 109.8, 99.8,
31.8 ppm; HRMS-ESI (m/z): calcd for C21H18NS, [M+H]+: 316.1154,
found 316.1148.
5-Methoxy-2-phenyl-3-(phenylthio)-1H-indole (3c).[9a] Yield: 86%; ESI (m/z): calcd for C17H17NNaS, [M+Na]+: 290.0974, found 290.0978.
1H NMR (400 MHz, CDCl3) δ 8.48 (s, 1H), 7.68 (d, J = 7.6 Hz, 2H), 7.43
- 7.32 (m, 3H), 7.25 (d, J = 8.4 Hz, 1H), 7.19 - 7.00 (m, 6H), 6.90 (d, J
2-Isobutyl-3-(phenylthio)-1H-indole (3j).[9a] Yield: 86%; 1H NMR
= 8.4 Hz, 1H), 3.76 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 155.2, 142.6,
139.3, 132.2, 131.4, 130.7, 128.9, 128.8, 128.6, 128.1, 125.5, 124.7,
113.8, 112.2, 101.2, 98.9, 55.9 ppm; HRMS-ESI (m/z): calcd for
C21H17NNaOS, [M+Na]+: 354.0923, found 354.0927.
(400 MHz, CDCl3) δ 8.16 (s, 1H), 7.54 (d, J = 7.6 Hz, 1H), 7.32 (d, J =
7.6 Hz, 1H), 7.18 (t, J = 7.6 Hz, 1H), 7.12 (dd, J = 9.6, 4.8 Hz, 3H), 7.03
(dd, J = 14.8, 7.6 Hz, 3H), 2.75 (d, J = 7.2 Hz, 2H), 1.98 (m, 1H), 0.90
(d, J = 6.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 144.5, 139.5, 135.5,
130.3, 128.6, 125.5, 124.5, 122.3, 120.6, 119.2, 111.0, 99.8, 35.6,
5-Fluoro-2-phenyl-3-(phenylthio)-1H-indole (3d).[9a] Yield: 66%; 1H 29.3, 22.5 ppm; HRMS-ESI (m/z): calcd for C18H19NNaS, [M+Na]+:
NMR (400 MHz, CDCl3) δ 8.41 (s, 1H), 7.64 (d, J = 7.2 Hz, 2H), 7.30 304.1130, found 304.1133.
(dd, J = 16.4, 7.6 Hz, 3H), 7.25 - 7.16 (m, 2H), 7.06 (t, J = 7.2 Hz, 2H),
3-(Phenylthio)-2-(thiophen-2-yl)-1H-indole (3k).[14a] Yield: 70%; 1H
NMR (400 MHz, CDCl3) δ 8.50 (s, 1H), 7.77 (s, 1H), 7.64 (d, J = 7.6 Hz,
1H), 7.57 (d, J = 4.8 Hz, 1H), 7.45- 7.31 (m, 2H), 7.24 - 7.19 (m, 1H),
7.13 (dt, J = 14.4, 7.6 Hz, 5H), 7.02 (t, J = 6.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 138.9, 137.7, 135.6, 132.1, 131.4, 128.8, 126.5, 126.3,
125.6, 124.6, 123.7, 123.4, 121.3, 119.7, 111.2, 99.1 ppm; HRMS-ESI
(m/z): calcd for C18H13NNaS2, [M+Na]+: 330.0382, found 330.0386.
6.97 (dd, J = 14.8, 7.6 Hz, 3H), 6.88 (t, J = 8.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 158.9 (d, J = 235.6 Hz), 143.9, 138.8, 132.4 (d, J = 2.5
Hz), 132.1, 129.0, 128.9, 128.7, 128.1, 125.7, 124.9, 112.2 (d, J = 9.5
Hz), 111.9 (d, J = 21.3 Hz), 105.0 (d, J = 24.0 Hz), 99.6 (d, J = 4.5 Hz)
ppm; HRMS-ESI (m/z): calcd for C20H14FNNaS, [M+Na]+: 342.0723,
found 342.0720.
1
5-Chloro-2-phenyl-3-(phenylthio)-1H-indole (3e).[9a] Yield: 72%; H
2-(Cyclohex-1-en-1-yl)-3-(phenylthio)-1H-indole (3l).[9a] Yield: 70%;
1H NMR (400 MHz, CDCl3) δ 8.28 (s, 1H), 7.56 (d, J = 7.6 Hz, 1H), 7.35
(d, J = 7.6 Hz, 1H), 7.24 - 6.93 (m, 8H), 6.35 (s, 1H), 2.63 - 2.54 (m,
NMR (400 MHz, CDCl3) δ 8.50 (s, 1H), 7.72 (d, J = 7.2 Hz, 2H), 7.51 (d,
J = 8.4 Hz, 1H), 7.48 - 7.34 (m, 4H), 7.18 - 7.11 (m, 3H), 7.08 - 7.00
(m, 3H); 13C NMR (100 MHz, CDCl3) δ 142.7, 138.9, 136.3, 131.0,
129.8, 129.4, 129.2, 128.9, 128.8, 128.1, 125.8, 124.9, 122.0, 120.9,
111.2, 100.0 ppm; HRMS-ESI (m/z): calcd for C20H14ClNNaS, [M+Na]+:
358.0428, found 358.0434.
2H), 2.25 - 2.19 (m, 2H), 1.78 - 1.72 (m, 2H), 1.68 - 1.63 (m, 2H); 13
C
NMR (100 MHz, CDCl3) δ 144.0, 139.8, 135.0, 131.2, 130.2, 129.3,
128.6, 125.5, 124.4, 122.8, 120.8, 119.5, 110.8, 97.9, 27.4, 25.7,
22.6, 21.9 ppm; HRMS-ESI (m/z): calcd for C20H19NNaS, [M+Na]+:
5-Bromo-2-phenyl-3-(phenylthio)-1H-indole (3f).[9a] Yield: 70%; 1H 328.1130, found 328.1126.
NMR (400 MHz, CDCl3) δ 8.50 (s, 1H), 7.68 (s, 1H), 7.66 (d, J = 6.8 Hz,
2-(3-(Phenylthio)-1H-indol-2-yl)aniline (3m).[9b] Yield: 60%; 1H NMR
(400 MHz, CDCl3) δ 8.72 (s, 1H), 7.60 (d, J = 7.6 Hz, 1H), 7.40 (d, J =
8.0 Hz, 1H), 7.28 (d, J = 7.2 Hz, 2H), 7.22 - 7.14 (m, 4H), 7.08 (d, J =
2H), 7.34 (dd, J = 15.6, 7.2 Hz, 3H), 7.25 (d, J = 8.8 Hz, 1H), 7.20 (d, J
= 8.4 Hz, 1H), 7.09 (t, J = 7.2 Hz, 2H), 7.00 (d, J = 7.6 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 143.4, 138.9, 134.5, 133.1, 130.9, 129.1,
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7.2 Hz, 2H), 7.04 (t, J = 7.0 Hz, 1H), 6.83 - 6.74 (m, 2H), 3.55 (s, 2H); ppm; HRMS-ESI (m/z): calcd for C22H16NaO3S, [M+NVai]e+w: A3rt8ic3le.0O7n1lin2e,
13C NMR (100 MHz, CDCl3) δ 144.8, 140.5, 138.8, 136.0, 131.4, 130.3, found 383.0718.
DOI: 10.1039/D0OB00828A
130.2, 128.7, 125.7, 124.6, 123.2, 121.0, 119.7, 118.8, 117.4, 116.5,
6-Bromo-2-phenyl-3-(phenylthio)benzofuran (5e).[9a] Yield: 73%; 1H
NMR (400 MHz, CDCl3) δ 8.19 (d, J = 7.2 Hz, 2H), 7.68 (s, 1H), 7.42
(dq, J = 14.0, 6.8 Hz, 3H), 7.35 - 7.27 (m, 2H), 7.20 - 7.15 (m, 4H),
111.2, 101.0 ppm; HRMS-ESI (m/z): calcd for C20H17N2S, [M+H]+:
317.1107, found 317.1105.
1
2-(4-Chlorophenyl)-3-(phenylthio)-1H-indole (3n).[9b] Yield: 77%; H 7.14 - 7.08 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 158.2, 154.1, 135.8,
NMR (400 MHz, CDCl3) δ 8.46 (s, 1H), 7.64 (t, J = 6.8 Hz, 3H), 7.45 - 130.0, 129.8, 129.3, 129.2, 128.7, 127.4, 127.0, 126.9, 125.9, 121.4,
7.34 (m, 3H), 7.27 (t, J = 7.6 Hz, 1H), 7.16 (dd, J = 14.4, 7.2 Hz, 3H), 118.7, 114.8, 105.1 ppm; HRMS-ESI (m/z): calcd for C20H13BrNaOS,
7.05 (dd, J = 15.6, 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 140.9, [M+Na]+: 402.9763, found 402.9756.
138.8, 135.8, 134.6, 131.2, 129.8, 129.2, 129.0, 128.8, 125.6, 124.8,
123.7, 121.4, 120.1, 111.2, 100.2 ppm; HRMS-ESI (m/z): calcd for
C20H14ClNNaS, [M+Na]+: 358.0428, found 358.0433.
6-Nitro-2-phenyl-3-(phenylthio)benzofuran (5f).[9a] Yield: 56%; 1H
NMR (400 MHz, CDCl3) δ 8.18 (d, J = 6.8 Hz, 2H), 8.06 (s, 1H), 7.94
(dd, J = 8.0, 1.2 Hz, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.51 - 7.38 (m, 6H),
2-(Naphthalen-2-yl)-3-(phenylthio)-1H-indole (3o).[21] Yield: 75%; 7.36 - 7.32 (m, 1H), 7.25 (t, J = 7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 8.16 (s, 1H), 7.92 - 7.85 (m, δ 158.5, 154.2, 148.9, 139.6, 131.8, 130.0, 129.8, 128.9, 127.4,
2H), 7.81 (m, 2H), 7.68 (d, J = 8.0 Hz, 1H), 7.52 - 7.45 (m, 2H), 7.43 (d, 125.6, 123.8, 120.8, 120.4, 120.0, 111.8, 102.8 ppm; HRMS-ESI
J = 8.0 Hz, 1H), 7.28 (t, J = 7.2 Hz, 1H), 7.18 (d, J = 8.0 Hz, 1H), 7.14 - (m/z): calcd for C20H13NNaO3S, [M+Na]+: 370.0508, found 370.0505.
7.10 (m, 4H), 7.04 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 141.8, 139.2,
3-((4-Methoxyphenyl)thio)-2-phenylbenzofuran (5g).[14a] Yield: 80%;
136.1, 133.2, 133.2, 131.4, 128.8, 128.5, 128.4, 127.9, 127.5, 126.8,
1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 7.6 Hz, 1H), 7.78 (s, 1H), 7.52
126.6, 125.8, 125.6, 124.7, 123.5, 121.3, 120.0, 111.1, 100.2 ppm;
HRMS-ESI (m/z): calcd for C24H18NS, [M+H]+: 352.1154, found
352.1158.
(d, J = 8.4 Hz, 1H), 7.48 (d, J = 7.6 Hz, 1H), 7.37 - 7.29 (m, 2H), 7.24 -
7.16 (m, 5H), 7.10 (dt, J = 8.4, 4.8 Hz, 1H), 6.96 (dd, J = 8.0, 1.6 Hz,
1H), 3.78 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.8, 157.5, 153.8,
2-(4-(tert-Butyl)phenyl)-3-(phenylthio)benzofuran (5a).[9a] Yield: 136.2, 130.9, 129.8, 129.1, 126.5, 125.8, 125.4, 123.6, 120.5, 120.0,
80%; 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 7.6 Hz, 2H), 7.56 (d, J = 115.9, 112.4, 111.4, 105.0, 55.4 ppm; HRMS-ESI (m/z): calcd for
8.0 Hz, 1H), 7.48 (d, J = 7.6 Hz, 3H), 7.35 (t, J = 7.6 Hz, 1H), 7.25 - C21H16NaO2S, [M+Na]+: 355.0763, found 355.0766.
7.18 (m, 5H), 7.13 - 7.08 (m, 1H), 1.35 (s, 9H); 13C NMR (100 MHz,
2-Phenyl-3-(p-tolylthio)benzofuran (5h).[13b] Yield: 90%; 1H NMR
CDCl3) δ 158.0, 153.8, 152.6, 136.4, 130.8, 129.0, 127.3, 127.0,
(400 MHz, CDCl3) δ 8.25 (d, J = 7.6 Hz, 2H), 7.53 (d, J = 8.0 Hz, 1H),
7.48 (d, J = 7.6 Hz, 1H), 7.42 (t, J = 7.2 Hz, 2H), 7.36 (d, J = 6.8 Hz,
1H), 7.29 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 7.6
Hz, 2H), 6.96 (d, J = 7.6 Hz, 2H), 2.23 (s, 3H); 13C NMR (100 MHz,
126.4, 125.8, 125.6, 125.0, 123.4, 120.3, 111.3, 103.9, 34.9, 31.3
ppm; HRMS-ESI (m/z): calcd for C24H22NaOS, [M+Na]+: 381.1284,
found 381.1287.
2-(4-Methoxyphenyl)-3-(phenylthio)benzofuran (5b).[14a] Yield: CDCl3) δ 157.2, 154.0, 135.5, 132.5, 131.1, 123.0, 129.8, 129.2,
84%; 1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 128.6, 127.4, 127.0, 125.2, 123.3, 120.6, 111.4, 105.4, 21.2 ppm;
8.0 Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.24 - HRMS-ESI (m/z): calcd for C21H16NaOS, [M+Na]+: 339.0814, found
7.16 (m, 5H), 7.13 - 7.06 (m, 1H), 6.95 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H); 339.0819.
13C NMR (100 MHz, CDCl3) δ 160.5, 157.8, 153.7, 136.5, 131.2, 129.2,
3-((4-Chlorophenyl)thio)-2-phenylbenzofuran (5i).[13b] Yield: 75%;
129.0, 126.3, 125.4, 124.8, 123.4, 122.4, 120.1, 114.2, 111.3, 102.6,
55.5 ppm; HRMS-ESI (m/z): calcd for C21H16NaO2S, [M+Na]+:
355.0763, found 355.0766.
1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 7.2 Hz, 2H), 7.54 (d, J = 8.0
Hz, 1H), 7.48 - 7.36 (m, 4H), 7.32 (t, J = 7.6 Hz, 1H), 7.22 (d, J = 7.6
Hz, 1H), 7.12 (q, J = 8.8 Hz, 4H); 13C NMR (100 MHz, CDCl3) δ 157.6,
2-(4-Chlorophenyl)-3-(phenylthio)benzofuran (5c).[22] Yield: 76%; 154.2, 134.7, 131.5, 130.6, 129.8, 129.5, 129.2, 128.7, 127.8, 127.5,
1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 7.2 Hz, 2H), 7.55 (d, J = 8.2 125.6, 123.7, 120.3, 111.3, 104.2 ppm; HRMS-ESI (m/z): calcd for
Hz, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.43 (d, J = 7.2 Hz, 2H), 7.35 (t, J = C20H13ClNaOS, [M+Na]+: 359.0268, found 359.0271.
7.6 Hz, 1H), 7.25 - 7.18 (m, 5H), 7.15 - 7.09 (m, 1H); 13C NMR (100
3-((4-Fluorophenyl)thio)-2-phenylbenzofuran (5j).[13b] Yield: 76%;
MHz, CDCl3) δ 156.5, 153.8, 135.7, 135.4, 130.7, 129.2, 128.8, 128.6,
1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 7.2 Hz, 2H), 7.52 (d, J = 8.0
128.3, 126.7, 125.6, 125.5, 123.5, 120.5, 111.6, 105.5 ppm; HRMS-
ESI (m/z): calcd for C20H13ClNaOS, [M+Na]+: 359.0268, found
359.0265.
Hz, 1H), 7.45 (t, J = 7.2 Hz, 3H), 7.40 (d, J = 7.2 Hz, 1H), 7.33 (t, J =
7.6 Hz, 1H), 7.24 - 7.15 (m, 3H), 6.89 (t, J = 8.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 161.2 (d, J = 243.6 Hz), 157.2, 154.0, 131.0 (d, J =
Methyl 2-phenyl-3-(phenylthio)benzofuran-5-carboxylate (5d).[9a] 3.2 Hz), 130.6, 129.7, 129.4, 128.7 (d, J = 8.3 Hz), 128.6, 127.4, 125.4,
Yield: 60%; 1H NMR (400 MHz, CDCl3) δ 8.28 - 8.22 (m, 3H), 8.08 (dd, 123.4, 120.3, 116.3 (d, J = 21.2 Hz), 111.4, 105.4 ppm; HRMS-ESI
J = 8.8, 1.6 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.50 - 7.43 (m, 3H), 7.24 - (m/z): calcd for C20H13FNaOS, [M+Na]+: 343.0563, found 343.0557.
7.18 (m, 4H), 7.16 - 7.08 (m, 1H), 3.90 (s, 3H); 13C NMR (100 MHz,
3-((3-Nitrophenyl)thio)-2-phenylbenzofuran (5k).[13b] Yield: 60%; 1H
CDCl3) δ 167.0, 158.9, 156.6, 135.9, 131.1, 129.8, 129.4, 129.2,
NMR (400 MHz, CDCl3) δ 8.16 (d, J = 7.6 Hz, 2H), 8.06 (d, J = 8.8 Hz,
2H), 7.612 (d, J = 8.0 Hz, 1H), 7.49 - 7.38 (m, 5H), 7.24 (t, J = 7.6 Hz,
128.7, 127.6, 127.1, 126.7, 126.0, 125.9, 122.8, 111.3, 105.3, 52.2
6 | J. Name., 2012, 00, 1-3
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3H); 13C NMR (100 MHz, CDCl3) δ 158.6, 154.2, 146.4, 145.6, 130.0,
129.3, 128.9, 127.4, 125.9, 125.8, 124.2, 123.8, 119.8, 111.8, 102.2
ppm; HRMS-ESI (m/z): calcd for C20H13NNaO3S, [M+Na]+: 370.0508,
found 370.0504.
10 (a) J. A. Joule, Indole and its Derivatives in Science of
Synthesis: Howben-Weyl Methods
of ViewMArtoiclleecOunllianer
DOI: 10.1039/D0OB00828A
Transformations; E. J. Thomas, Ed.; George Thieme: Stuttgart,
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R. Ragno, A. Coluccia, G. La Regina, G. De Martino, F. Piscitelli,
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
We thank the Ministry of Science and Technology of the People’s
Republic of China (2016YFA0602900), the National Natural
Science Foundation of China (21971072 and 21672072), the
Fundamental Research Funds for the Central Universities
(2018ZD16), the Pearl River S&T Nova Program of Guangzhou
(201906010072), Guangdong Provincial Training Program of
Innovation and Entrepreneurship for Undergraduates
(S201910561219), and the Open Fund of Guangdong Provincial
Key Laboratory of Luminescence from Molecular Aggregates
(2019B030301003) for financial support.
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