Forging C-S Bonds through Nickel-Catalyzed Aryl Anhydrides with Thiophenols: Decarbonylation or Decarbonylation Accompanied by Decarboxylation

Article abstract of DOI:10.1021/acs.joc.9b01746

A nickel-catalyzed decarbonylation or decarbonylation accompanied by decarboxylation cross-coupling reaction of aryl anhydrides with thiophenols as coupling partners was disclosed. This method is promoted by a commercially available, moisture-stable, and inexpensive nickel(II) precatalyst. The process can tolerate a variety of functional groups using ubiquitous aryl anhydrides as cross-coupling precursors to produce thioethers in moderate to excellent yields.

Full text of DOI:10.1021/acs.joc.9b01746

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Article
Forging C-S Bonds through Nickel-Catalyzed Aryl
Anhydrides with Thiophenols : Decarbonylation or
Decarbonylation Accompanied by Decarboxylation
Jing-Ya Zhou, Shou-Wei Tao, Rui-Qing Liu, and Yong-Ming Zhu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01746 • Publication Date (Web): 29 Aug 2019
Downloaded from pubs.acs.org on August 29, 2019
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Forging C-S Bonds through Nickel-Catalyzed
Aryl Anhydrides with Thiophenols :
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Decarbonylation
or
Decarbonylation
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Accompanied by Decarboxylation
Jing-Ya Zhou, Shou-Wei Tao, Rui-Qing Liu, Yong-Ming Zhu*
College of Pharmaceutical Sciences, Soochow University, Suzhou 215123, China
*E-mail: zhuyongming@suda.edu.cn
Abstract
A nickel-catalyzed decarbonylation or decarbonylation accompanied by decarboxylation
cross-coupling reaction of aryl anhydrides with thiophenols as coupling partners was disclosed. This
method is promoted by a commercially-available, moisture-stable and inexpensive nickel(II)
precatalyst. The process can tolerate a variety of functional groups, using ubiquitous aryl anhydrides
as cross-coupling precursors to produce thioethers in moderate to excellent yields.
Introduction
Aryl sulfides are an important motif, frequently found in biologically and pharmaceutically active
compounds (Figure 1).1 They are also used in advanced materials and industrial chemicals such as
organic semiconductors, herbicides, lubricants, and high boiling point solvents.2 Therefore, the
development of effective C-S bonds construction methods is still receiving widespread attention. The
cross-coupling reactions of aryl halides with thiols and arylboronic acids with thiols are representative
methods for constructing C-S bonds.3 In recent years, the method of constructing C-S bonds by
decarbonylation has attracted people’s attention. Many research groups have explored the principle of
decarbonylation and used several excellent transition metals such as Pd,4 Rh,5 Ir,6 and Ni7 to drive the
reaction forward. In recent years, there has been an increasing interest in nickel catalysis because of its
non-toxic, environmentally friendly and lower price. For example, in 2017, Eric W. Reinheimer and
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Jessie Weatherly8 reported the first systematic study of Ni(0) precursor Ni(COD)2 catalyzed
decarbonylation of aromatic aldehydes (Scheme 1, a). In the same year, Marc A. Hillmyer and
William B. Tolman9 reported that nickel catalyzed the decarbonylation of carboxylic acids to olefins
(Scheme 1, b). Recently, Magnus Rueping's group10 developed a method for decarbonylation using a
stable nickel source (II) as a catalyst (Scheme 1, c). At the same time, Chengwei Liu and Michal
Szostak11 had the same research discoverys (Scheme 1, d). Therefore, nickel-catalyzed cross-coupling
reactions have become a rapidly growing field in synthetic chemistry. However, conventional
decarbonylation reactions typically use Ni(0) catalysts12 that are sensitive to air and moisture, which
makes the reaction conditions somewhat limited. Both Magnus Rueping and Michal Szostak's research
teams used air-stable, easy-to-handle and manipulable NiCl2 and dppp catalytic systems to
successfully decarbonylate to give thioethers. Therefore, our laboratory considers the use of aryl
anhydrides that are easy to synthesize and widely exist in nature as aryl sources, and utilizes the
nucleophilicity of S to obtain thioethers.
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Figure 1. Examples of pharmaceutically-relevant aryl thioethers
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Scheme 1. Application of nickel in decarbonylation
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Results and Discussion
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The reaction was optimized using benzoic anhydride and naphthalene-2-thiol as model substrates.
Considering economic factor and stability to air and moisture, we chose nickel (II) as a catalyst. Key
optimization experiments are summarized in Table 1.
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Table 1. Optimization of Reaction Condition[a]
Ni cat.
(mol%)
NiCl2
Ligand
(mol%)
dppp
dppp
dppp
dppp
dppp
dppp
dppp
dppp
dppp
dppp
dppe
Pcy3
Entry
Solvent
Base
Additive
Yield
toluene
toluene
toluene
toluene
1,4-dioxane
DMSO
DMF
K2CO3
Cs2CO3
Na2CO3
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mn
Mg
Zn
19%
23%
95%
28%
55%
30%
40%
80%
76%
83%
76%
83%
85%
64%
67%
1
NiCl2
2
NiCl2
3
NiCl2
4
/
NiCl2
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
5
NiCl2
6
NiCl2
7
Ni(OAC)2·H2O
Ni(acac)2
NiBr2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
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15
NiCl2
NiCl2
NiCl2
dppf
NiCl2
dppp
dppp
NiCl2
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NiCl2
dppp
toluene
Na2CO3
72%
16
/
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8
[a]General conditions: the reactions were run on a 0.5 mmol of naphthalene-2-thiol in solvent (1.5 mL),
benzoic anhydride (1.2 equiv.), catalyst (10 mol%), ligand (20 mol%), base (0.2 equiv.), additive (1
equiv.) under nitrogen in a sealed tube at 150°C for 24 h. Isolated yield after purification of column
chromatography.
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When the reaction was run in the presence of NiCl2 (10 mol%), dppp (20 mol%), K2CO3 (0.2 equiv.)
and reducing agents Mn in toluene for 24
h
under nitrogen, the desired product
naphthalen-2-yl(phenyl)sulfane was obtained in 19 % yield (Table 1, entry 1). To our delight, the yield
was raised to 95% when inorganic base Na2CO3 was used (Table1, entry 3). Compared with other
commercially available bases, Na2CO3 was optimal for this reaction. In addition, without adding alkali,
the reaction does not work well (Table 1, entries 1–4). The results indicated that a suitable inorganic
base played an important role in the decarbonylation process. Solvent screening revealed that when the
polarity of the solvent increased, the amount of by-products also increased, and the raw materials
couldn’t be completely reacted. Toluene was clearly superior to other solvents (Table 1, entries 5-7).
Compared with other nickle sources, NiCl2 was optimal for this reaction (Table 1, entries 8-10).
Switching to other ligands, such as dppe, pcy3, or dppf, yield was reduced compared to dppp ligand
(Table 1, entries 11–13). In order to determine the role of the reducing agent in the reaction, we
replaced different reducing agents, such as Mg, Zn. It was found that Mn had the best reactivity in this
reaction (Table 1, entries 14–16). Thus, the best conditions for this reaction were thiophenol(1 equiv.),
aryl anhydride (1.2 equiv), NiCl2 (10 mol%) and dppp (20 mol%) as the catalyst system, with Na2CO3
(0.2 equiv) as the base and toluene as the solvent under nitrogen atmosphere at 150°C.
Having optimized the reaction conditions, the substrate scope of this nickle-catalyzed decarbonylation
reaction was investigated. As illustrated in Table 2, a wide variety of reactants bearing either
electron-withdrawing or electron-donating substituents on the aryl ring could be transformed into the
corresponding compounds 3 in moderate to excellent yields. Halogens, methyl, methoxyl, aryl,
aliphatic groups were well-tolerated in this system, and yielded desired products over 80% (Table 2,
entries 1−11). The steric hindrance does not have much effect on the yield (Table 2, 3c, 3k).
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Table 2. Reactions of different aryl anhydrides with 2-naphthylthiophenol to
synthesize various Aryl sulfides.[a,b]
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Entry Substrate
Product
Yield[b]
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92%
3a
1a
2
99%
89%
94%
95%
96%
3b
1b
3
1c
3c
4
3d
1d
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3e
3f
1e
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1f
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99%
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80%
82%
98%
96%
3h
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[a]General conditions: the reactions were run on a 0.5 mmol of naphthalene-2-thiol under nitrogen in a
sealed tube, using 1 (1.2 equiv.), NiCl2 (10 mol%), dppp (20 mol%), Mn(2 equiv.), Na2CO3 (0.2 equiv.)
in toluene (1.5 mL) at 150 °C for 24 h. [b] Isolated yields.
Next, we explored the flexibility of the method for various thiophenols or thiols, using
4-Methoxyphenyl anhydride as a substrate (Table 3). Both electron-rich and electron-poor groups were
effectively decarbonylated to get thioethers. And the electron-withdrawing decreases with respect to
the yield of electron donating groups (Table 3, 4c-4g). In addition, the steric hindrance effect has little
effect on the yield (Table 3, 4i, 4j). Fortunately, aliphatic thiols gave the corresponding products in
moderate to high yields (Table 3, 4k, 4l).
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Table 3. Reactions of different thiophenols or thiols with 4-methoxybenzoic
anhydride to synthesize various aryl sulfides.[a,b]
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Entry
Substrate
Product
Yield[b]
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92%
2a
3a
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8
96%c
83%
75%
52%
71%
74%
85%
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2c
2d
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4c
4d
4e
2e
2f
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2g
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99%
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83%c
88%c
70%c
4j
2j
2k
4k
2l
4l
[a]General conditions: the reactions were run on a 0.5 mmol of thiophenols under nitrogen in a sealed
tube, using 1a (1.2 equiv.), NiCl2 (10 mol%), dppp (20 mol%), Mn(2 equiv.), Na2CO3 (0.2 equiv.) in
toluene (1.5 mL) at 150 °C for 24 h. [b] Isolated yields. [c] 170 °C and 48 h
We also apply this method to phthalic anhydride, but only a small amount of target products were
produced, most of which were self-coupling products, so we changed the original conditions.
Considering that the dppp ligand can also act as a reducing agent in this reaction, first we reacted at
150°C for 48 hours without adding a manganese reducing agent. Found that there were fewer target
products and self-couplig products were also observed, but surprisingly there was a large amount of
thioester formed (Table 4, 3e’). This result indicates that the reaction is also feasible for the cyclic
anhydride, and the principle of the reaction is that the decarbonylation is accompanied by
decarboxylation. In order to improve the yield, we further optimized reaction conditions. It was found
that after increasing the ratio of the catalyst to the ligand and the amount of the base, the reaction
proceeded well, yielding 89% of the desired product. Therefore, we explored the coupling reaction of
phthalic anhydride with other thiophenols.
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Table 4. Reactions of different thiophenols with phthalic anhydride to synthesize
various aryl sulfides.[a,b]
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Entry
Substrate
Product
3e
Yield[b]
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tracec
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2a
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6
89%
52%d
67%
61%
66%
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2c
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5d
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63%
64%
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[a]General conditions: the reactions were run on a 0.5 mmol of thiophenols under nitrogen in a sealed
tube, using 1m (1.2 equiv.), NiCl2 (15 mol%), dppp (60 mol%), Na2CO3 (4.5 equiv.) in toluene (1.5
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7
[b]
[c]
mL) at 170 °C for 48 h.
Isolated yields.
Under the conditions of NiCl2 (10 mol%), dppp (20
8
9
mol%), Na2CO3 (0.2 equiv.) at 150 °C, 74% of the S-(naphthalen-2-yl) benzothioate (3e’) was
obtained. [d] 72 h
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As shown in Table 4, the excellent yield was obtained when the substrate is naphthalene-2-thiol (Table
4, 3e). Moderate yield can be obtained when an electron withdrawing group is present on the benzene
ring (Table 4, 5c-5e). Similarly, we also reacted phthalic anhydride with naphthalene-1-thiol and
2-methylbenzenethiol to examine the effect of steric hindrance on the reaction and also to obtain
moderate yields (Table 4, 5i, 5m). When the electron donating group is attached to the thiophenol ring,
the reaction time is extended to 72 hours, and a moderate yield can be obtained (Table 4, 5b).
Therefore, we have also made substrate expansion for other cyclic anhydrides, such as diphenic
anhydride and naphthalic anhydride. It was unexpectedly discovered that biphenyl anhydride and
naphthalene anhydride could also get thioethers. For biphenyl anhydride, the carboxyl groups on the
biphenyl cannot be removed due to the non-coplanarity of the two benzene rings. Thus, the carboxyl
group forms a thioester with thiophenol, which is then decarbonylated to generate a disulfide product.
(Scheme 2, 6a, 6i). Because of the large steric hindrance of the naphthalene-2-thiol, the yield of
disulfide produced is lower (Scheme 2, 6a). And 2-methylthiophenol has less steric hindrance relative
to naphthalene-2-thiol, so the yield is relatively high (Scheme 2, 6i). This method is also applicable to
naphthalic anhydride. However, due to the large steric hindrance of the naphthalene ring, the carboxyl
group can be removed, and finally a monosulfide product is formed. The yield of monosulfide product
obtained by the reaction of naphthalene-2-thiol with naphthalic anhydride can reach 56% (Scheme 2,
7a). The yield of o-methylthiophenol with higher steric hindrance is lower (Scheme 2, 7i).
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Scheme 2. Reactions of different thiophenols with cyclic anhydrides to synthesize
aryl sulfides.[a,b]
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Scheme 3. Gram-Scale Reaction of 3f
To prove the practicality of this method as a synthetic tool, we also performed scale-up production of
3f. In this case, product 3f was obtained in 82% yield, indicating good scalability of the reaction.
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Scheme 4. Mechanistic Experiments
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To deeper explore the reaction mechanism, we tested the mechanism of the reaction between
monoanhydride and thiophenol. When the reaction was carried out at 130 °C for 12 hours, we
observed the formation of the target product thioether and intermediate thioester. (Scheme 4, a).
Therefore, we believe that the reaction mechanism of monoanhydride may proceed in two paths. At
the same time, We used benzoic 4-methoxybenzoic anhydride as a raw material for the reaction, and
found that a mixture of the two products was obtained (Scheme 4, b). In addition, we investigated
whether nickel participates in the decarboxylation process of phthalic anhydride (Scheme 4, c). We
have found that in the reaction without nickel, a large amount of thioester is obtained. This result
indicates that nickel may not participate in the decarboxylation process in this reaction.
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Scheme 5. Plausible Mechanism for the Synthesis of thioethers
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According to previous literature reports10, 13-17 and control experiments, a plausible mechanism for the
Ni(II)-catalyzed anhydrides reacting with thiophenols is shown in Scheme 5. Initially, carbon dioxide
is removed from anhydride A to form thioester C with thiophenol in the presence of base. At the same
time, NiII is reduced to be LnNi0 E by the reducing reagent. The C-S bond of thioester C is oxidatively
added with LnNi0 complex E to give acyl nickel (II) intermediate G. Anhydride D forms acyl nickel
(II) intermediate G through two paths. The anhydride D can be converted into a thioester intermediate
C by the action of thiophenol and a base, followed by oxidative addition to obtain an acyl nickel
compound G, or first oxidative addition with LnNi0 E to obtain a compound F through the path B, then
attack by the phenyl sulfide anion to give compound G. Acyl nickel (II) intermediate G is
decarbonylated to obtain intermediate H. Finally, the C-S bond formation by reductive elimination
provides the thioether and the active catalyst (Ni0).
Conclusion
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In summary, we have developed a novel and convenient nickel-catalyzed decarbonylation or
decarbonylation as well as decarboxylation protocol which allows the transfer of a series of readily
available aromatic anhydrides to the corresponding thioether. This provides a new way to effectively
build C-S bonds. More interestingly, we found that dibasic anhydride could also be used as an aryl
source, through decarbonylation accompanied by decarboxylation, finally give the thioether. Various
thiophenols and a wide range of aromatic anhydrides bearing various substituents are tolerated in this
process, which afforded products in moderate to excellent yields.
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EXPERIMENTAL SECTION
General Information. In addition to benzoic anhydride, other monoanhydrides were prepared
according to previously reported methods.18 Reactants and reagents were purchased from commercial
suppliers and used without further purification. All anhydrous solvents used in the reactions were dried
and freshly distilled. TLC was performed on silica HSGF254 plates. Melting points were determined
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with a digital melting-point apparatus. H (400 MHz) and 13C(101 or 151 MHz) NMR spectra were
obtained from solutions in CDCl3 or with tetramethylsilane as an internal standard using 400 or 600
MHz spectrometers. High-resolution mass spectra (HRMS) analyses were carried out on a chemical
ionization (CI) apparatus using time-of-flight (TOF) mass spectrometry.
General Procedure for the Synthesis of Aryl Sulfide[3a-3l, 4a-4k]: Thiophenol (0.5mol),
Anhydride (0.6 mmol), NiCl2 (7 mg, 0.05 mmol), Dppp (41 mg, 0.1 mmol), Mn (55 mg, 1 mmol), and
Na2CO3 (11 mg, 0.1 mmol) were successively added into a 15 mL sealed tube, using anhydrous
toluene (1.5 mL) as solvent. The mixture was stirred in a 150 °C oil bath under nitrogen for 24 h.
Upon completion of the reaction as indicated by TLC, the mixture was diluted with EtOAc, and then
filtered through a pad of Celite. The solvent was removed under vacuum. The residue was purified on
a silica gel column (petroleum ether) to give the pure target product.
General Procedure for the Synthesis of Aryl Sulfide[5a-5m, 6a, 6i, 7a, 7i ]:Thiophenol (0.5 mol),
Anhydride (0.6 mmol), NiCl2 (12 mg, 0.09 mmol), Dppp (148 mg, 0.36 mmol), and Na2CO3 (286 mg,
2.7 mmol) were successively added into a 15 mL sealed tube, using anhydrous toluene (1.5 mL) as
solvent. The mixture was stirred in a 170 °C oil bath under nitrogen for 48 h. Upon completion of the
reaction as indicated by TLC, the mixture was diluted with EtOAc, and then filtered through a pad of
Celite. The solvent was removed under vacuum. The residue was purified on a silica gel column
(petroleum ether) to give the pure target product.
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4-Methoxybenzoic anhydride(1a)18a White solid (8578 mg, 94%). H NMR (400 MHz, CDCl3) δ 8.10
(d, J = 8.8 Hz, 4H), 6.98 (d, J = 8.8 Hz, 4H), 3.90 (s, 6H).
4-Methylbenzoic anhydride(1b)18b White solid (458 mg, 88%). 1H NMR (400 MHz, CDCl3) δ 8.04 (d,
J = 7.6 Hz, 4H), 7.32 (d, J = 7.6 Hz, 4H), 2.46 (s, 6H).
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2-Methylbenzoic anhydride(1c)18b White solid (416 mg, 80%). 1H NMR (400 MHz, CDCl3) δ 8.05 (d,
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J = 8.0 Hz, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.37 – 7.30 (m, 4H), 2.70 (s, 6H).
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3-Methylbenzoic anhydride(1d)18b Yellow solid (442 mg, 85%). 1H NMR (400 MHz, CDCl3) δ 7.96 (s,
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2H), 7.95 (d, J = 7.2 Hz, 2H), 7.48 (d, J = 7.2 Hz, 2H), 7.41 (t, J = 7.2 Hz, 2H), 2.45 (s, 6H).
2-Naphthoic anhydride(1f)18b White solid (568 mg, 85%). 1H NMR (400 MHz, CDCl3) δ 8.79 (s, 2H),
8.20 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.99 (d, J = 8.4 Hz, 3H), 7.95 (d, J = 8.4 Hz, 2H),
7.68 (t, J = 7.2 Hz, 2H), 7.61 (t, J = 7.2 Hz, 2H).
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3,5-Dimethoxybenzoic anhydride(1g)18b Yellow oil (610 mg, 86%). H NMR (400 MHz, CDCl3) δ
7.26 (s, 4H), 6.75 (s, 2H), 3.85 (s, 12H).
4-Chlorobenzoic anhydride(1h)18b White solid (566 mg, 86%). 1H NMR (400 MHz, CDCl3) δ 8.08 (d,
J = 8.4 Hz, 4H), 7.52 (d, J = 8.4 Hz, 4H).
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3-Chlorobenzoic anhydride(1i)18b White solid (506 mg, 84%). H NMR (400 MHz, CDCl3) δ 8.11 (s,
2H), 8.04 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 8.0 Hz, 2H), 7.50 (t, J = 7.6 Hz, 2H).
Cinnamic anhydride(1j)18b White solid (456 mg, 80%). 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 16.0
Hz, 2H), 7.59 (m, 4H), 7.50 – 7.37 (m, 6H), 6.54 (d, J = 16.0 Hz, 2H).
2-Methoxybenzoic anhydride(1k)18b Yellow oil (539 mg, 92%). 1H NMR (400 MHz, CDCl3) δ 8.00 (m,
2H), 7.58 – 7.51 (m, 2H), 7.02 (m, 4H).
(4-Methoxyphenyl)(naphthalen-2-yl)sulfane (3a)19 White solid (122 mg, 92%); mp 69.3-71.5 °C. H
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NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.2 Hz, 1H), 7.69 (m, 2H), 7.59 (s, 1H), 7.49 – 7.38 (m, 4H),
7.29 (d, J = 8.7 Hz, 1H), 6.92 (d, J = 8.4 Hz, 2H), 3.84 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ
160.0 (s),136.0 (s), 135.4 (s), 133.9 (s), 131.9 (s), 128.7 (s), 127.8 (s), 127.3 (s), 126.9 (s), 126.7 (s),
126.6 (s), 125.8 (s), 124.6 (s), 115.2 (s), 55.5 (s). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
C17H14OS 267.0844; Found 267.0843.
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Naphthalen-2-yl(p-tolyl)sulfane (3b)10 White solid (124 mg, 99%); mp 68.7-71.9 °C. H NMR (400
MHz, CDCl3) δ 7.78 (d, J = 7.6 Hz, 1H), 7.76 – 7.66 (m, 3H), 7.50 – 7.40 (m, 2H), 7.34 (m, 3H), 7.15
(d, J = 7.6 Hz, 2H), 2.36 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ 137.8 (s), 134.5 (s), 134. 0(s),
132.3 (s), 132.2 (s), 131.5 (s), 130.2 (s), 128.8 (s), 128.5 (s), 128.1 (s), 127.9 (s), 127.4 (s), 126.7 (s),
126.1 (s), 21.3 (s)
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Naphthalen-2-yl(o-tolyl)sulfane (3c)20 Light yellow oil (111mg, 89%). H NMR (400 MHz, CDCl3) δ
7.82 – 7.77 (m, 1H), 7.75 (d, J = 9.2 Hz, 1H), 7.69 (d, J = 6.7 Hz, 1H), 7.65 (s, 1H), 7.45 (m, 2H), 7.32
(t, J = 7.2 Hz, 3H), 7.23 (d, J = 7.2 Hz, 1H), 7.15 (t, J = 7.2 Hz, 1H), 2.41 (s, 3H); 13C{1H} NMR (151
MHz, CDCl3) δ 140.1 (s), 134.0 (s), 134.0 (d, J = 15.3 Hz), 133.9 (s), 133.7 (s), 133.1 (s), 132.1 (s),
130.8 (s), 128.9(s), 128.2 (s), 128.2 (d, J = 20.4 Hz), 128.2 (d, J = 20.4 Hz), 127.9 (s), 127.9 (d, J = 4.8
Hz), 127.8 (s), 127.4 (s), 126.9 (s), 126.7 (s), 126.0 (s), 20.8 (s).
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Naphthalen-2-yl(m-tolyl)sulfane (3d)3d White solid (118 mg, 94%); mp 61.4-66.0 °C. H NMR (400
MHz, CDCl3) δ 7.85 – 7.69 (m, 4H), 7.51 – 7.42 (m, 2H), 7.40 (d, J = 8.8 Hz, 1H), 7.24 – 7.15 (m,
3H), 7.07 (d, J = 6.4 Hz, 1H), 2.31 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ 139.3 (s), 135.5 (s),
133.9 (s), 133.5 (s), 132.4 (s), 131.9 (s), 129.7 (s), 129.2 (s), 128.9 (s), 128.8 (s), 128.4 (s), 128.2(s),
127.9 (s), 127.5 (s), 126.7 (s), 126.3 (s), 21.5 (s).
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Naphthalen-2-yl(phenyl)sulfane (3e)19 White solid (112 mg, 95%); mp 54.2-56.9 °C. H NMR (400
MHz, CDCl3) δ 7.84 (s, 1H), 7.83 – 7.79 (m, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.75 – 7.70 (m, 1H), 7.52 –
7.43 (m, 2H), 7.43 – 7.35 (m, 3H), 7.31 (t, J = 7.2 Hz, 2H), 7.26 (d, J = 7.6 Hz, 1H); 13C{1H} NMR
(101 MHz, CDCl3) δ 136.0 (s), 133.9 (s), 133.1 (s), 132.4 (s), 131.1 (s), 130.0 (s), 129.4 (s),129.0 (s),
128.9 (s), 127.9 (s), 127.6 (s), 127.2 (s), 126.7 (s), 126.3 (s).
S-(naphthalen-2-yl) benzothioate (3e’)11 White solid (98 mg, 74%). H NMR (400 MHz, CDCl3) δ
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8.07 (d, J = 6.0 Hz, 3H), 7.96 – 7.82 (m, 3H), 7.63 (t, J = 7.2 Hz, 1H), 7.59 – 7.47 (m, 5H); 13C{1H}
NMR (101 MHz, CDCl3) δ 190.5 (s), 136.8 (s), 135.1 (s), 133.9 (s), 133.8 (s), 133.6 (s), 131.6 (s),
129.0 (s), 128.9 (s), 128.2 (s), 128.0 (s), 127.7 (s), 127.3 (s), 126.7 (s), 124.8 (s).
Di(naphthalen-2-yl)sulfane (3f)21 White solid (137 mg, 96%); mp 154.7-155.2 °C. 1H NMR (400 MHz,
CDCl3) δ 7.88 (s, 2H), 7.85 – 7.80 (m, 2H), 7.78 (d, J = 8.7 Hz, 2H), 7.76 – 7.69 (m, 2H), 7.53 – 7.45
(m, 4H), 7.44 (d, J = 8.6 Hz, 2H); 13C{1H} NMR (151 MHz, CDCl3) δ 134. 0(s), 133.2 (s), 132.5 (s),
129.9 (s), 129.0 (s), 128.8 (s), 127.9 (s), 127.6 (s), 126.8 (s), 126.4 (s).
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(3,5-Dimethoxyphenyl)(naphthalen-2-yl)sulfane (3g) Light yellow oil (147 mg, 99%). H NMR (400
MHz, CDCl3 ) δ 7.90 (s, 1H), 7.84 – 7.80 (m, 1H), 7.80 – 7.73 (m, 2H), 7.53 – 7.46 (m, 2H), 7.44 (d, J
= 8.4 Hz, 1H), 6.50 (d, J = 1.6 Hz, 2H), 6.34 (s, 1H), 3.73 (s, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ
161.2 (s), 138.2 (s), 133.9 (s), 132.6 (s), 132.2 (s), 130.8 (s), 129.3 (s), 129.0 (s), 127.9 (s), 127.7 (s),
126.7 (s), 126.5 (s), 108.4 (s), 99.6 (s), 55.6 (s). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
C18H16O2S 297.0949; Found 297.0947.
(4-Chlorophenyl)(naphthalen-2-yl)sulfane (3h)3c White solid (108 mg, 80%); mp 108.5-110.1 °C. H
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NMR (400 MHz, CDCl3) δ 7.84 (s, 1H), 7.78 (m, 3H), 7.53 – 7.45 (m, 2H), 7.38 (d, J = 8.8 Hz, 1H),
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7.27 (s, 4H); 13C{1H} NMR (101 MHz, CDCl3) δ 134.8 (s), 133.9 (s), 133.2 (s), 132.6 (s), 132.4 (s),
132.1 (s), 130.5 (s), 129.5 (s), 129.2 (s), 128.9 (s), 127.9 (s), 127.6 (s), 126.9 (s), 126.6 (s).
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(3-Chlorophenyl)(naphthalen-2-yl)sulfane (3i)22 White solid (111 mg, 82%); mp 64.3-68.5 °C. H
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NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.88 – 7.74 (m, 3H), 7.55 – 7.47 (m, 2H), 7.43 (d, J = 8.8 Hz,
1H), 7.28 (s, 1H), 7.19 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ 139.0 (s), 135.1 (s), 133.9 (s),
132.8 (s), 131.7 (s), 131.2 (s), 130.3 (s), 129.6 (s), 129.4 (s), 128.0 (d, J = 11.4 Hz), 127.7 (s), 126.9
(s), 126.9 (s), 126.8 (s).
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Naphthalen-2-yl(styryl)sulfane (3j)23 White solid (128 mg, 98%); mp 79.4-81.3 °C. H NMR (400
MHz, CDCl3) δ 7.86 (s, 1H), 7.84 – 7.74 (m, 3H), 7.53 – 7.43 (m, 3H), 7.38 (d, J = 7.2 Hz, 2H), 7.33
(t, J = 7.2 Hz, 2H), 7.25 (t, J = 8 Hz, 2H), 6.98 (d, J = 15.2 Hz, 1H), 6.80 (d, J = 15.6 Hz, 1H); 13C{1H}
NMR (101 MHz, CDCl3) δ 136.7 (s), 134.0 (s), 132.8 (s), 132.4 (s), 132.34 (s), 128.9 (s), 128.9 (s),
128.4 (s), 127.9 (s), 127.8 (s), 127.8 (s), 127.5 (s), 126.9 (s), 126.3 (s), 123.3 (s).
(2-Methoxyphenyl)(naphthalen-2-yl)sulfane (3k) Light yellow oil (80 mg, 60%). 1H NMR (400 MHz,
CDCl3) δ 7.83 (s, 1H), 7.82 – 7.70 (m, 3H), 7.51 – 7.44 (m, 2H), 7.41 (d, J = 8.4 Hz, 1H), 7.25 (t, J =
8.4 Hz, 2H), 7.11 (d, J = 7.6 Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H), 6.87 (t, J = 7.5 Hz, 1H), 3.88 (s, 3H);
13C{1H} NMR (151 MHz, CDCl3) δ 157.5 (s), 134.0 (s), 132.5 (s), 132.0 (s), 131.8 (s), 130.4 (s),
129.2 (s), 128.9 (s), 128.5 (s), 127.9 (s), 127.6 (s), 126.6 (s), 126.3 (s), 124.2 (s), 121.4 (s), 111.1 (s),
56.1 (s). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C17H14OS 267.0844; Found 267.0836.
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Bis(4-methoxyphenyl)sulfane (4b)24 Yellow solid (118 mg, 96%); mp 49.5-50.1 °C. H NMR (400
MHz, CDCl3) δ 7.27 (d, J = 8.8 Hz, 4H), 6.83 (d, J = 8.4 Hz, 4H), 3.79 (s, 6H); 13C{1H} NMR (101
MHz, CDCl3) δ 159.2 (s), 132.9 (s), 127.6 (s), 114.9 (s), 55.5 (s).
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(4-Fluorophenyl)(4-methoxyphenyl)sulfane (4c)25 Colorless oil (97 mg, 83%). H NMR (400 MHz,
CDCl3) δ 7.36 (d, J = 8.4 Hz, 2H), 7.24 – 7.15 (m, 2H), 6.95 (t, J = 8.8 Hz, 2H), 6.88 (d, J = 8.4 Hz,
2H), 3.81 (s, 4H); 13C{1H} NMR (101 MHz, CDCl3) δ 161.8 (d , J C-F = 247.0 Hz ) , 159.9 (s), 134.6
(s), 133.3 (d, J C-F = 3.3 Hz), 131.3 (d, J C-F= 8.0 Hz), 125.5 (s), 116.2 (d , J C-F = 22.0 Hz ) , 115.2 (s),
55.5 (s).
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(4-Chlorophenyl)(4-methoxyphenyl)sulfane(4d)26 Yellow solid (94 mg, 75%); mp 63.9-64.2 °C. H
NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 8.4 Hz, 2H),
6.90 (d, J = 8.4 Hz, 2H), 3.83 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.2 (s), 137.5 (s), 135.6
(s), 131.8 (s), 129.5 (s), 129.2 (s), 124.0 (s), 115.3 (s), 55.5 (s).
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(4-Methoxyphenyl)(4-(trifluoromethyl)phenyl)sulfane (4e)27 Light yellow oil (74 mg, 52%). H NMR
(400 MHz, CDCl3) δ 7.45 (dd, J = 13.2, 8.4 Hz, 4H), 7.13 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H),
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3.85 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.8 (s), 145.0 (s), 136.8 (s), 127.4 (q, J C-F = 32.6
Hz), 126.6 (s), 125.8 (q, J C-F = 3.4 Hz), 124.3 (q, J C-F = 272.1 Hz), 121.8 (s), 115.5 (s), 55.6 (s).
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(3,4-Difluorophenyl)(4-methoxyphenyl)sulfane (4f) Light yellow oil (89 mg, 71%). H NMR (400
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NMR (101 MHz, CDCl3) δ 160.4 (s), 150.6 (dd, J C-F = 251.7 Hz, J C-F = 13.4 Hz), 149.0 (dd, J
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248.6 Hz, J C-F = 12.9 Hz), 135.8 (s), 135.4 (q, J = 3.5 Hz), 124.2 (q, J C-F = 3.5 Hz), 123.7 (s), 117.8 (d,
J C-F = 17.5 Hz), 117.3 (d, J C-F = 19.0 Hz), 115.4 (s), 77.16 (s), 55.6 (s). HRMS (ESI-TOF) m/z: [M +
H]+ Calcd for C13H10F2OS 253.0499; Found 253.0500.
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(3-fluorophenyl)(4-methoxyphenyl)sulfane (4g)28 Colorless oil (87 mg, 74%). H NMR (400 MHz,
CDCl3) δ 7.45 (d, J = 8.4 Hz, 2H), 7.22 – 7.13 (m, 1H), 6.96 – 6.87 (m, 3H), 6.84 – 6.72 (m, 2H), 3.84
(s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 163.2 (d, J C-F =248.6 Hz), 160.5 (s), 141.9 (d, J C-F = 7.6
Hz), 136.4 (s), 130.2 (d, J C-F = 8.6 Hz), 122.9 (d, J C-F = 3.0 Hz), 122.8 (s), 115.4 (s), 114.2 (d, J C-F
23.7 Hz), 112.4 (d, J C-F = 21.4 Hz), 55.5 (s).
=
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(4-Methoxyphenyl)(p-tolyl)sulfane (4h)26 Yellow solid (98 mg, 85%); mp 46.1-47.1°C. H NMR (400
MHz, CDCl3) δ 7.36 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 7.06 (d, J = 7.6 Hz, 2H), 6.87 (d, J
= 8.4 Hz, 2H), 3.81 (s, 3H), 2.30 (s, 3H); 13C{1H} NMR (151 MHz, cdcl3) δ 159.6 (s), 136.3 (s), 134.5
(s), 134.5 (s), 129.9 (s), 129.5 (s), 125.8 (s), 115.0 (s), 55.5 (s), 21.1 (s).
(4-Methoxyphenyl)(o-tolyl)sulfane (4i)26 Light yellow oil (114 mg, 99%). 1H NMR (400 MHz, CDCl3)
δ 7.33 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.2 Hz, 1H), 7.13 – 7.02 (m, 2H), 6.97 (d, J = 7.2 Hz, 1H), 6.89
(d, J = 8.0 Hz, 2H), 3.82 (s, 3H), 2.38 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 159.7 (s), 137.3 (s),
137.2 (s), 134.7 (s), 130.4 (s), 129.3 (s), 126.6 (s), 126.3 (s), 124.7 (s), 115.2(s), 55.5 (s), 20.4 (s).
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3-((4-Methoxyphenyl)thio)-2-methylfuran (4j) Yellow oil (91 mg, 83%). H NMR (400 MHz, CDCl3)
δ 7.32 (s, 1H), 7.13 (d, J = 8.4 Hz, 2H), 6.80 (d, J = 8.8 Hz, 2H), 6.33 (s,1H), 3.77 (s, 3H), 2.36 (s, 3H).
13C{1H} NMR (101 MHz, CDCl3) δ 158.4 (s), 155.8 (s), 141.2 (s), 129.5 (s), 128.4(s), 115.3 (s), 114.8
(s), 109.9 (s), 55.5 (s), 12.0 (s). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C12H12O2S 221.0636;
Found 221.0637.
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Cyclohexyl(4-methoxyphenyl)sulfane (4k)29 Light yellow oil (98 mg, 88%). H NMR (400 MHz,
CDCl3) δ 7.38 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 3.80 (s, 3H), 2.89 (m, 1H), 1.93 (m, 2H),
1.75 (m, 2H), 1.60 (m, 1H), 1.33 – 1.21 (m, 6H); 13C{1H} NMR (151 MHz, CDCl3) δ 159.4 (s), 135.7
(s), 125.1 (s), 114.4 (s), 55.5 (s), 48.1 (s), 33.5 (s), 26.3 (s), 25.9 (s).
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Benzyl(4-methoxyphenyl)sulfane (4l)30 White solid (81 mg, 70%); mp 48.3-48.6 °C. H NMR (400
MHz, CDCl3) δ 7.27 – 7.17 (m, 7H), 6.79 (d, J = 8.0 Hz, 2H), 3.98 (s, 2H), 3.78 (s, 3H); 13C{1H}
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NMR (151 MHz, CDCl3) δ 159.4 (s), 138.3 (s), 134.2 (s), 129.0 (s), 128.5 (s), 127.1 (s), 126.2 (s),
114.6 (s), 55.5 (s), 41.4 (s).
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(4-Methoxyphenyl)(phenyl)sulfane (5b)3b Yellow oil (19 mg, 17%). H NMR (400 MHz, CDCl3) δ
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7.42 (d, J = 8.4 Hz, 2H), 7.22 (m, 2H), 7.20 – 7.10 (m, 3H), 6.90 (d, J = 8.4 Hz, 2H), 3.82 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 160.0 (s), 138.7 (s), 135.5 (s), 129.1 (s), 128.4 (s), 125.9 (s),
124.6 (s), 115.2 (s), 55.5 (s).
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(4-Fluorophenyl)(phenyl)sulfane (5c)11 Colorless oil (68 mg, 67%). H NMR (400 MHz, CDCl3) δ
7.38 (dd, J = 8.1, 5.5 Hz, 2H), 7.33 – 7.28 (m, 2H), 7.27 – 7.17 (m, 3H), 7.02 (t, J = 8.1 Hz, 2H); 13C
NMR (151 MHz, CDCl3) δ 163.4 (s), 161.7 (s), 136.8 (s), 134.2 (d, J = 8.2 Hz), 131.2 (s), 130.1 (s),
129.3 (s), 126.9 (s), 116.6 (s), 116.5 (s); 13C{1H} NMR (101 MHz, CDCl3) δ 162.5 (d, J C-F= 248.5Hz),
136.8 (s), 134.2 (d, J
= 8.4 Hz), 130.3 (d, J C-F= 3.4 Hz), 130.1 (s), 129.3 (s), 126.9 (s), 116.6 (s),
C-F
116.4 (s).
(4-Chlorophenyl)(phenyl)sulfane (5d)11 White solid (67 mg, 61%); mp 49.7-52.6 °C. 1H NMR
(400MHz, CDCl3) δ 7.37 – 7.21 (m, 9H); 13C{1H} NMR (101 MHz, CDCl3) δ 135.3 (s), 134.8 (s),
133.2 (s), 132.2 (s), 131.5 (s), 129.5 (d, J = 1.8 Hz), 127.6 (s).
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Phenyl(4-(trifluoromethyl)phenyl)sulfane (5e)11 Colorless oil (84 mg, 66%). H NMR (400 MHz,
CDCl3) δ 7.52 – 7.42 (m, 5H), 7.39 (d, J = 5.3 Hz, 3H), 7.28 (s, 1H); 13C NMR (101 MHz, CDCl3)
δ143.0 (s),133.7 (s), 132.70 (s), 129.8 (s), 128.8 (s), 128.5 (s), 128.1 (s), 126.0 (q, J C-F= 3.8 Hz),
122.9(s); 13C{1H} NMR (101 MHz, CDCl3) δ 142.98 (d, J C-F = 1.2 Hz), 133.7 (s), 132.7 (s), 131.2 (s),
129.8 (s), 128.8 (s), 128.5 (s), 1260. (q, J C-F = 3.8 Hz), 125.6 (s), 122.9 (s).
phenyl(o-tolyl)sulfane (5i)11 Colorless oil (63 mg, 63%). 1H NMR (400 MHz, CDCl3) δ 7.32 – 7.09 (m,
9H), 2.37 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.1 (s), 136.3 (s), 133.9 (s), 133.2 (s), 130.7
(s), 129.8 (s), 129.3 (s), 128.04 (s), 126.8 (s), 126.5 (s), 20.7 (s).
naphthalen-1-yl(phenyl)sulfane(5m)3b Colorless oil (75 mg, 64%). 1H NMR (400 MHz, CDCl3) δ 8.42
– 8.34 (m, 1H), 7.86 (m, 2H), 7.67 (d, J = 7.2 Hz, 1H), 7.52 (m, 2H), 7.43 (t, J = 8 Hz, 1H), 7.27 –
7.16 (m, 5H); 13C{1H} NMR (101 MHz, CDCl3) δ 137.0 (s), 134.4 (s), 133.7 (s), 132.7 (s), 131.3 (s),
129.3 (s), 129.2 (s), 129.1 (s), 128.7 (s), 127.08 (s), 126.6 (s), 126.3 (s), 126.0 (s), 125.8 (s).
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2,2'-Bis(naphthalen-2-ylthio)-1,1'-biphenyl (6a)31 Yellow solid (80 mg, 34%); mp 175.9-176.6 °C. H
NMR (400 MHz, CDCl3) δ 7.76 (s, 4H), 7.68 (d, J = 8.0 Hz, 4H), 7.44 (m, 4H), 7.35 (d, J = 8.4 Hz,
2H), 7.25 (m, 8H); 13C{1H} NMR (151 MHz, CDCl3) δ 141.3 (s), 136.4 (s), 133.9 (s), 132.8 (s), 132.5
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(s), 131.2 (s), 131.1 (d, J = 21.2 Hz), 131.1 (s), 130.8 (s), 129.7 (s), 128.9 (s), 128.8 (d, J = 19.4 Hz),
128.7 (s), 127.8 (s), 127.6 (s), 126.6 (s), 126.6 (d, J = 14.4 Hz), 126.5 (s), 126.3 (s).
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2,2'-Bis(o-tolylthio)-1,1'-biphenyl (6i)31 White solid (117 mg, 59%); mp 148.7-152.1 °C. H NMR
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(400 MHz, CDCl3) δ 7.39 (m, 2H), 7.21 (m, 10H), 7.14 (s, 2H), 6.96 – 6.88 (m, 2H), 2.31 (s, 6H);
13C{1H} NMR (101 MHz, CDCl3) δ 141.3 (s), 140.1 (s), 137.2 (s), 134.7 (s), 133.5 (s), 130.7 (s),
130.5 (s), 128.6 (s), 128.6 (s), 128.4 (s), 126.8 (s), 125.7 (s), 20.8 (s).
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Naphthalen-1-yl(naphthalen-2-yl)sulfane (7a)32 White solid (80 mg, 56%); mp 48.3-48.6 °C. H NMR
(400 MHz, CDCl3) δ 7.87 (s, 2H), 7.85 - 7.67 (m, 7H), 7.55 - 7.36 (m, 7H); 13C{1H} NMR (101 MHz,
CDCl3) δ 134.0 (s), 133.3 (s), 132.5 (s), 130.0 (s), 129.1 (s), 128.8 (s), 127.9 (s), 127.6 (s), 126.8 (s),
126.4 (s).
1
Naphthalen-1-yl(o-tolyl)sulfane (7i)33 Light yellow oil (36 mg, 29%). H NMR (400 MHz, CDCl3) δ
8.33 (m, 1H), 7.88 (m, 1H), 7.84 – 7.77 (m, 1H), 7.53 (m, 2H), 7.43 – 7.35 (m, 2H), 7.25 – 7.21 (m,
1H), 7.14 (t, J = 7.2 Hz, 1H), 7.02 (t, J = 7.6 Hz, 1H), 6.94 (d, J = 7.6 Hz, 1H), 2.46 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 138.4 (s), 135.0 (s), 134.3 (s), 133.2 (s), 132.1 (s), 130.9 (s), 130.6 (s),
130.4 (s), 128.7 (s), 128.4 (s), 127.0 (s), 126.9 (s), 126.8 (s), 126.5 (s), 126.0 (s), 125.4 (s), 20.6 (s).
ASSOCIATED CONTENT
AUTHOR IMF OR MATION
Corresponding Author
*E-mail: zhuyongming@suda.edu.cn
ORCID
Yong-Ming Zhu: 0000-0002-7078-7908
NOTES
The author declare no competing financial interest
Supporting Information
Supporting Information Figures giving 1H, 13C NMR spectra.
ACKNOWLEDGMENTS
We gratefully acknowledge the financial support by PAPD (A Project Funded by the
Priority Academic Program Development of Jiangsu Higher Education Institutions).
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