Copper/Nickel-Catalyzed Selective C–S/S–S Bond Formation Starting from O-Alkyl Phenylcarbamothioates

Article abstract of DOI:10.1002/ejoc.201901884

A convenient and effective method is described to construct C–S/S–S bond starting from O-alkyl phenylcarbamothioates, giving diverse O-alkyl S-phenyl phenylcarbonimidothioates and isothiourea disulfides, respectively. The C–S bond formation products (O-al

Full text of DOI:10.1002/ejoc.201901884

A Journal of
Accepted Article
Title: Copper/Nickel-Catalyzed Selective C-S/S-S Bond Formations
Starting from O-alkyl Phenylcarbamothioates
Authors: Kang Peng, Ming-Yuan Gao, Yu-Yan Yi, Jia Guo, and Zhi-
Bing Dong
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901884
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10.1002/ejoc.201901884
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Copper/Nickel-Catalyzed Selective C-S/S-S Bond Formations
Starting from O-alkyl Phenylcarbamothioates
Kang Peng,[a] Ming-Yuan Gao,[a] Yu-Yan Yi,[a] Jia Guo,[b],[c] and Zhi-Bing Dong*[a],[b],[c],[d]
Abstract: A convenient and effective method is described to
In recent decades, environmentally friendly reaction media,
construct C-S/S-S bond starting from O-alkyl phenylcarbamothioates, especially water, has received widespread attention because of
giving diverse O-alkyl S-phenyl phenylcarbonimidothioates and
isothiourea disulfides, respectively. The C-S bond formation
products (O-alkyl S-phenyl phenylcarbonimidothioates) were
synthesized by using Cu2O as catalyst in water (without phase
transfer catalyst), and the S-S bond formation product (isothiourea
disulfides) could be furnished catalyzed by NiBr2 at room
temperature. These transformations feature easy control,
environmental friendliness, and good to excellent yields, which could
be attractive in the selective C-S/S-S bond formation.
its green nature and low price.[8] On the other hand, recent
studies on copper-catalyzed C-S coupling reactions in water
have made significant progress,[9] while phase transfer catalysts
(PTC) are often required for most reported protocols.[10] Recently,
we reported the palladium-catalyzed synthesis of 2-
aminobenzothiazoles
promoted
by
iodobenzene
via
intramolecular coupling (Scheme 1, A).[11] Lately, we found that
the reaction could be catalyzed by NiBr2 very quickly (Scheme 1,
B).[12] Inspired by these work, we believed that O-methyl
phenylcarbamothioates could also be transformed by a similar
intramolecular oxidation. Unexpectedly, the target cyclization
product was not obtained (Scheme 1, C), and the isothiourea
disulfides were detected (Scheme 1, D), and we also noticed
that no S-S formation product was generated in the presence of
PhI(OAc)2 without adding NiBr2. While we tried this model
reaction by using cheap copper salt as catalyst and
iodobenzene as “promoter”, the S-arylation product was formed
(Scheme 1, E). As part of our longstanding interest in C-S bond
formation and the related applications,[13] we wish to report here
an efficient and selective method for the C-S/S-S formation by
using O-alkyl phenylcarbamothioates as starting materials.
Introduction
The sulfur-containing organic compounds have great chemical
and biological significance as synthetic intermediates.[1] As one
of them, thiocarbamate derivatives are not only important
structures in biological systems, but also common derivatives in
medical research.[2] They could be served as anti-tumour agents
(a),[3] anti-diabetic agents (b),[4] and anti-breast cancer agent
(c).[5] In addition, S-substituted thiocarbamates also show very
interesting biological effects, for example, S-glycosyl O-methyl
phenylcarbamothioates can be new promising building blocks in
the synthesis of oligosaccharides to give glycosyl donors (d)
(Figure 1).[6] On the other hand, organic compounds containing
S-S bonds are normally the key motifs to stabilize proteins.[7]
Therefore, the study on S-substituted thiocarbamates via C-S
bond formation and disulfides via S-S bond formation has
attracted more and more attention from synthetic chemists and
biologists.
Figure 1. Representative S-substituted thiocarbamates with biological activity.
Scheme 1. Selective C-S/S-S bond formations starting from O-alkyl
phenylcarbamothioate.
[a]
School of Chemistry and Environmental Engineering, Wuhan
Institute of Technology, Wuhan 430205, China.
[b]
[c]
[d]
Key Laboratory of Green Chemical Process, Ministry of Education,
Wuhan Institute of Technology, Wuhan 430205, China.
Hubei Key Laboratory of Novel Reactor and Green Chemistry Techn
ology, Wuhan Institute of Technology, Wuhan 430205, China.
Ministry-of-Education Key Laboratory for the Synthesis and
Application of Organic Functional Molecules, Hubei University,
Wuhan 430062, China.
Results and Discussion
To optimize the S-arylation reaction conditions, different copper
catalysts
were
initially
screened
using
O-methyl
phenylcarbamothioate 1a and aryl iodide 2a (Table 1, entries 1-
Email: dzb04982@wit.edu.cn
5) as starting materials. The results showed that Cu2O was
https://cee.wit.edu.cn/info/1052/1538.htm
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10.1002/ejoc.201901884
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superior to CuI, CuBr, Cu(OAc)2, and CuCl2, and providing 3a in
71% yield (entry 3). The reaction was hardly to proceed in the
absence of the copper catalyst or base, indicating that the
catalyst and base are crucial (entries 6-7). Then the effect of
bases were evaluated (entries 3, 8−13), and K2CO3 was proved
to be the optimal. Subsequently, examination of base loading
showed that increasing the amount of base to 3 equiv. led to
almost no yield change, whereas decreasing the base loading to
1 equiv. led to a significant decrease in yield (entries 14–15).
Among these, 2 equiv. of base loading was found to be optimal.
The screening of copper also revealed that the yield of the
reaction was significantly reduced when the catalyst loading of
copper was reduced to 2.5 mol% (entry 16). To our delight,
further solvent screening showed that the reaction could be
conducted in water (entries 17-19), giving the S-arylation
product in 69% yield, which was just in line with the concept of
green chemistry. Various ligands were also screened to improve
the reaction yields (entries 20-24), and 1,10-phenanthroline was
found to be the most effective. Finally, the reaction temperature
was screened (entries 25-26). Thus, the optimized reaction
With the optimal reaction conditions established, a series of aryl
iodides and O-methyl phenylcarbamothioate were surveyed to
investigate the substrate range of the S-arylation reaction. The
results are shown in Table 2. To our delight, substituted aryl
iodides could couple with O-methyl phenylcarbamothioate in
moderate to excellent yields. Generally, aryl iodides bearing with
electron-donating groups in the para, meta, or ortho position
gave products 2a-2h in moderate to excellent yields (entries 1-7).
Meanwhile, substrates with electron-withdrawing groups such as
Cl- or Br- could give target compounds with excellent yields
(entries 9-13), and substrates with strong electron-withdrawing
groups (NO2, CN, CF3) also give moderate to good yields
(entries 8, 14-15). In addition, 2-iodothiophene was also
investigated, and products 3p was afforded in excellent yield
(94%), which showed its good substrate compatibility.
Table 2. S-Arylation of O-methyl phenylcarbamothioate with various aryl
iodides.[a]
conditions
were
summarized
as
follows,
O-methyl
phenylcarbamothioates (1a, 0.5 mmol) and aryl iodides (2a, 0.6
mmol), CuI (5 mol%), 1,10-phenanthroline (10 mol%) and K2CO3
(2.0 equiv.) in water (2 mL) at 100°C stirred for 4 hours (entry
22).
Entry
Aryl iodide
Product
Yield[b](%)
1
91
Table 1. Optimization of reaction conditions for the synthesis of 3a.[a]
2a
3a
3b
2
3
96
88
2b
2c
T
Yield
[%][b]
61
38
71
Entry
Catalyst
Base
Ligand
Solvent
[°C]
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
80
1
2
3
4
5
6
7
8
9
10
11
12
13
14[c]
15[d]
16[e]
17
18
19
20
21
22
23
24
25
26
CuI
CuBr
Cu2O
Cu(OAc)2
CuCl2
Cu2O
-
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
-
K2CO3
KOH
NaOH
t-BuOK
CH3ONa
Et3N
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
DMAC
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
47
54
3c
3d
N.R.
trace
trace
60
trace
27
57
52
55
73
58
62
58
69
86
62
91
65
4
5
79
85
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
2d
NaH
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
2e
2f
3e
3f
-
-
-
6
7
78
82
BPy
Py
1,10-phen
L-Proline
TMEDA
1,10-phen
1,10-phen
66
72
92
2g
120
3g
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.6 mmol), catalyst (5 mol%),
ligand (10 mol%), base (2.0 equiv.), solvent (2 mL), stirred for 4 hours at
100°C. [b] Isolated yield. [c] Base (1.0 equiv.). [d] Base (3.0 equiv.). [e]
Catalyst (2.5 mol%).
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Table 3. S-Arylation of aryl iodide with various O-alkyl
phenylcarbamothioates.[a]
8
81
91
2h
3h
O-methyl
9
Entry
Product
Yield[b](%)
phenylcarbamothioate
2i
2j
3i
1
98
10
11
12
82
93
91
1b
3r
3j
2
3
87
89
1c
1d
2k
3k
3s
3t
2l
3l
13
14
15
95
65
56
2m
4
5
6
95
92
83
3m
3n
1e
3u
3v
2n
1f
2o
2p
3o
3p
16
94
1g
3w
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.6 mmol), catalyst (5 mol%),
ligand (10 mol%), base (2.0 equiv.), solvent (2 mL), stirred at 100°C for 4
hours. [b] Isolated yield.
[a] Reaction conditions: 1a (0.5 mmol), 2a (0.6 mmol), catalyst (5 mol%),
ligand (10 mol%), base (2.0 equiv.), solvent (2 mL), stirred at 100°C for 4
hours. [b] Isolated yield.
Studies
on
the
scope
of
a
series
of
O-alkyl
In order to further expand the substrates range of C-S coupling
(halogenated compounds), we tried to replace aryl iodide by
methyl iodide and aryl bromide, and the corresponding target
products were obtained in 86% and 38% yields (Scheme 2).
phenylcarbamothioates reacting with iodo benzene were
summarized in Table 3. The reaction showed good functional
compatibility in general, and a series of O-alkyl (alkly=methyl,
ethyl) S-phenyl phenylcarbonimidothioates were furnished
smoothly
in
good
to
excellent
yields.
O-alkyl
phenylcarbamothioates bearing with halide groups, such as Cl
gave the intended products in 87% (3s) and 92% (3v),
respectively. Substrate with electron-withdrawing group, such as
NO2 was also suitable to give 3w in good yield, substrate with
electron-donating substituents (MeO-) showed good results as
well (3r, 3u).
Scheme 2. C-S coupling between methyl iodide, aryl bromide and O-alkyl
phenylcarbamothioate.
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As mentioned in the introduction part, the reaction conditions
shown in Scheme 1 (B)12 were subsequently applied to a variety
of O-alkyl phenylcarbamothioates, giving the selective S-S bond
formation compounds (isothiourea disulfides) with 75-87% yields
(Table 4). The results revealed that the electronic nature of the
aryl ring has little effects on these oxidative homo-coupling
reactions.
Table 4. S-S bond formation of various O-alkyl phenylcarbamothioates.[a]
O-alkyl
phenylcarbamothioate
Entry
Product
Yield[b](%)
Scheme 3. Possible mechanism for the S-arylation of O-alkyl
phenylcarbamothioates.
1
82
1a
4a
Conclusions
2
3
4
87
75
78
1d
1f
4b
4c
In conclusion, we have developed a practical method to
construct
C-S/S-S
bonds
starting
from
O-alkyl
phenylcarbamothioates.
A
series of O-methyl S-phenyl
phenylcarbonimidothioate derivatives were synthesized in water
with Cu2O as catalyst and without phase transfer catalyst, and
the corresponding isothiourea disulfides could also be obtained
by using NiBr2 as catalyst. The method has advantages of easy
control, environmental friendliness and good to excellent yields,
which is expected to find industrial and academic applications in
the future. The detailed reaction mechanism and the related
applications of this protocol are under research in our lab.
1h
4d
[a] Reaction conditions: 1 (0.5 mmol), NiBr2 (1 mol%), PhI(OAc)2 (1.0 equiv.),
pyridine (2.0 equiv.), 1,4-dioxane (2 mL), open air, stirred at r.t. for 10 min. [b]
Isolated yield.
Although the mechanism of S-arylation reaction at present is not
Experimental Section
clear, we proposed
a possible path way based on the
experimental results and the previous references,[14] which was
outlined in Scheme 3. The first step of the reaction is to
generate a catalytically active Cu(II) complex A from Cu2O, 1,10-
phenanthroline, water and K2CO3 in air. Then iodobenzene and
Cu(II) complex A undergoes oxidation addition reaction to form
intermediate B. Next, disproportionation between the two copper
species B and subsequent ligand displacement of the O-methyl
phenylcarbamothioate continue to form Cu(III) intermediate C.
Finally, reductive elimination of C gives the coupling product D,
with regeneration of Cu2O.
As for the mechanism of oxidative homo-coupling (not proceed
ortho cyclization) of O-methyl phenylcarbamothioate, we
speculate that the withdrawing nature of the methoxy group
promotes the activity of the SH (a dynamic equibrium from NH
group of the thiourea), which would proceed the homo-coupling
easily, instead of the ortho C-H activation with higher energy
barrier.
General remarks: Flash column chromatography was operated on silica
gel with petroleum ether-EtOAc (PE-EA) as the eluent. Thin layer
Chromatography was adopted and visualized under UV light. The RY-1G
instrument was adopted to determine melting points of target compounds.
The HRMS (high-resolution mass spectra) was recorded from a Finnigan
MAT 95Q mass instrument (ESI). A Bruker AM400 NMR instrument was
operated in CDCl3 to record NMR spectra.
Typical procedure for the preparation of O-alkyl S-phenyl
phenylcarbonimidothioates (TP1): O-methyl phenylcarbamothioate
(0.5 mmol), aryl iodide (0.6 mmol), Cu2O (5 mol%), 1,10-phenanthroline
(10 mol%) and K2CO3 (1.0 mmol) were added in a dried sealed tube
equipped with a septum and magnetic stirring bar, H2O (2.0 mL) was
then added. The mixture was stirred at 100oC and checked by TLC until
the starting material was finished (about 4 h). The reaction was
quenched with sat. NH4Cl solution (3.0 mL) and then extracted with ethyl
acetate. The crude solution was dried over anhydrous Na2SO4 and
evaporated under vacuum. The residue was purified by flash column
chromatography to afford the desired product.
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Typical procedure for the preparation of isothiourea disulfides
(TP2): O-methyl phenylcarbamothioate (0.5 mmol), PhI(OAc)2 (0.5 mmol),
NiBr2 (1 mol%) were added in a dried sealed tube equipped with a
septum and magnetic stirring bar, 1,4-dioxane (2.0 mL) was then
added. The mixture was stirred at room temperature and checked by
TLC until the starting material was finished (about 10 min.). The reaction
was quenched with sat. NH4Cl solution (3.0 mL) and then extracted with
ethyl acetate. The crude solution was dried over anhydrous Na2SO4 and
evaporated under vacuum. The residue was purified by flash column
chromatography to afford the desired product.
silica gel (petroleum ether/ethyl acetate = 10:1) to give the target
compound 3f 106 mg (yield: 78 %), a white solid. M.p.: 92-94℃. 1H NMR
(400 MHz, CDCl3): δ: 7.45 (d, J = 8.0 Hz, 2 H), 7.38 (t, J = 8.0 Hz, 2H),
7.13 (t, J = 8.0 Hz, 1H), 7.02 (d, J = 8.0 Hz, 2H), 6.90 (d, J = 8.0 Hz, 2H),
3.88 (s, 3H), 3.84 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 160.4,
157.7, 147.3, 136.9, 129.0, 123.8, 121.7, 119.2, 114.5, 56.4, 55.3 ppm.
HRMS (ESI) m/z [M+H]+ Calcd for C15H16NO2S (274.0896); found:
274.0902.
S-(2-methoxyphenyl) O-methyl phenylcarbonimidothioate (3g):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3g 112 mg (yield: 82 %), a white solid. M.p.: 130-132℃. 1H
O-methyl S-phenyl phenylcarbonimidothioate (3a): According to TP1,
the residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 15:1) to give the target compound 3a 111 mg (yield:
NMR (400 MHz, CDCl3): δ: 7.48 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 8.0 Hz,
3H), 7.15 (t, J = 8.0 Hz, 1H), 7.08 (d, J = 8.0 Hz, 2H), 6.98-6.92 (m, 2H),
3.92 (s, 3H), 3.87 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 159.4,
157.4, 147.6, 136.5, 131.1, 129.0, 123.8, 121.8, 120.8, 117.5, 111.3,
56.3, 56.0 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C15H16NO2S
(274.0896); found: 274.0892.
91 %), a white solid. M.p.: 92-94℃. 1H NMR (400 MHz, CDCl3): δ = 7.57-
7.54 (m, 2H), 7.43-7.38 (m, 5H), 7.20-7.16 (m, 1H), 7.06-7.03 (m, 2H),
3.90 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.0, 147.2, 135.2,
129.1, 129.0 128.9, 128.8, 123.9, 121.7, 56.4ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C14H14NOS (244.0791); found: 244.0798.
O-methyl S-phenyl p-tolylcarbonimidothioate (3b): According to TP1,
the residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 20:1) to give the target compound 3b 123 mg (yield:
96 %), a white solid. M.p.: 86-88℃. 1H NMR (400 MHz, CDCl3 ): δ = 7.38
O-methyl S-(4-(trifluoromethyl)phenyl) phenylcarbonimidothioate
(3h): According to TP1, the residue was purified by flash chromatography
on silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
compound 3h 126 mg (yield: 81 %), a white solid. M.p.: 84-86℃. 1H NMR
(m, J = 8.0 Hz, 4H), 7.16 (m, J =8.0 Hz, 3H), 7.02 (d, J =4.0 Hz, 2H), 3.88
(s, 3 H), 2.40 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.4, 147.2,
139.2, 135.2, 129.7, 129.0, 125.2, 123.8, 121.7, 56.4, 21.3 ppm. HRMS
(ESI) m/z [M+H]+ Calcd for C15H16NOS (258.0947); found: 258.0941.
(400 MHz, CDCl3): δ = 7.63-7.58 (m, 4H), 7.37 (t, J = 8.0 Hz, 2H), 7.15 (t,
J = 8.0 Hz, 1H), 6.98 (d, J = 8.0 Hz, 2H), 3.90 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3): δ = 155.5, 146.7, 135.1, 133.7, 131.0, 129.1, 125.6, 125.5
(q, JC-F = 270 Hz), 124.1, 121.6, 56.6 ppm. HRMS (ESI) m/z [M+H]+
Calcd for C15H13F3NOS (312.0665); found: 312.0669.
O-methyl S-(o-tolyl) phenylcarbonimidothioate (3c): According to TP1,
the residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 20:1) to give the target compound 3c 113 mg (yield:
88 %), a colorless oil. 1H NMR (400 MHz, CDCl3 ): δ = 7.54 (d, J = 8.0 Hz,
1H), 7.41 (t, J =8.0 Hz, 2H), 7.33 (m, J =8.0 Hz, 2H), 7.19 (m, J =8.0 Hz,
2H), 7.06 (m, J =8.0 Hz, 2H), 3.88 (s, 3H), 2.48 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 157.3, 147.4, 142.5, 136.4, 129.7, 128.4, 126.4,
123.9, 121.6, 56.3, 21.1 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C15H16NOS (258.0947); found: 258.0955.
S-(4-chlorophenyl)
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3i 126 mg (yield: 91 %), a white solid. M.p.: 116-120℃. 1H
NMR (400 MHz, CDCl3): δ = 7.32 (d, J = 8.0 Hz, 2H), 7.27-7.20 (m, 4H),
7.04 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 8.0 Hz, 2H), 3.77(s, 3H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 155.3, 145.8, 135.4, 134.4, 128.0, 126.2,
122.9, 120.6, 55.5 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C14H13ClNOS
(278.0401); found: 278.0408.
O-methyl
phenylcarbonimidothioate
(3i):
S-(3,4-dimethylphenyl) O-methyl phenylcarbonimidothioate (3d):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
compound 3d 107 mg (yield: 79 %), a white solid. M.p.: 80-82℃. 1H NMR
S-(2-chlorophenyl)
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
O-methyl
phenylcarbonimidothioate
(3j):
(400 MHz, CDCl3 ): δ = 7.39 (t, J = 8.0 Hz, 2H), 7.29 (t, J =8.0 Hz, 2H),
7.16 (t, J =8.0 Hz, 2H), 7.02 (d, J =4.0 Hz, 2H), 3.90 (s, 3H), 2.30 (d, J
=8.0 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.6, 147.3, 137.9,
137.3, 136.3, 132.8, 130.2, 129.0, 125.2, 123.8, 121.7, 56.4, 19.7, 19.6
ppm.HRMS (ESI) m/z [M+H]+ Calcd for C16H18NOS (272.1104); found:
272.1092.
compound 3j 114 mg (yield: 82 %), a white solid. M.p.: 68-70℃. 1H NMR
(400 MHz, CDCl3): δ = 7.46 (d, J = 8.0 Hz, 1H), 7.36 (d, J =8.0 Hz, 1H),
7.26.-7.18 (m, 3H), 7.11 (t, J =8.0 Hz, 1H), 7.02 (t, J =8.0 Hz, 1H), 6.91
(d, J =8.0 Hz, 2H), 3.75 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ =
154.9, 146.1, 138.1, 135.9, 129.5, 128.9, 127.9, 127.5, 125.9, 122.9,
120.5, 55.4 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C14H13ClNOS
(278.0401); found: 278.0395.
S-(3,5-dimethylphenyl) O-methyl phenylcarbonimidothioate (3e):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
compound 3e 115 mg (yield: 85 %), a white solid. M.p.: 78-80℃. 1H NMR
S-(4-bromophenyl)
O-methyl
phenylcarbonimidothioate
(3k):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
(400 MHz, CDCl3): δ: 7.37 (t, J = 8.0 Hz, 2H), 7.15 (t, J = 8.0 Hz, 3H),
7.00 (d, J = 4.0 Hz, 3H), 3.90 (s, 3H), 2.34 (s, 6H) ppm. 13C NMR (100
MHz, CDCl3): δ = 157.4, 157.3, 138.4, 132.8, 130.8, 129.0, 128.0, 123.8,
121.7, 56.4, 21.2 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C16H18NOS
(272.1104); found: 272.1112.
compound 3k 149 mg (yield: 93 %), a white solid. M.p.: 132-136℃. 1H
NMR (400 MHz, CDCl3): δ = 7.37 (d, J = 8.0 Hz, 2H), 7.27-7.23 (m, 4H),
7.04 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 8.0 Hz, 2H), 3.37 (s, 3H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 155.1, 145.8, 135.6, 130.9, 128.0, 126.8,
122.9, 122.6, 120.5, 55.5 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C14H13BrNOS (321.9896); found: 321.9904.
S-(4-methoxyphenyl) O-methyl phenylcarbonimidothioate (3f):
According to TP1, the residue was purified by flash chromatography on
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10.1002/ejoc.201901884
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S-(3-bromophenyl)
O-methyl
phenylcarbonimidothioate
(3l):
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3q 134 mg (yield: 98 %), a yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.39-7.37 (m, 2H), 7.24-7.18 (m, 3H), 6.84-6.77 (m, 4H), 3.72
(s, 3H), 3.68 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.1, 155.2,
139.2, 134.1, 127.9, 127.8, 127.7, 121.5, 113.5, 55.3, 54.3 ppm. HRMS
(ESI) m/z [M+H]+ Calcd for C15H16NO2S (274.0896); found: 274.0901.
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3l 146 mg (yield: 91 %), a colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.55 (s, 1 H), 7.37 (d, J = 8.0 Hz, 1H), 7.31 (t, J = 8.0 Hz, 1H),
7.24 (t, J = 8.0 Hz, 2H), 7.10-7.00 (m, 2H), 6.86 (d, J = 4.0 Hz, 2H), 3.76
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.9, 145.7, 136.5, 132.6,
130.9, 129.7, 129.0, 127.9, 122.9, 121.2, 55.5 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C14H13BrNOS (321.9896); found: 321.9888.
O-methyl
S-phenyl
(4-chlorophenyl)carbonimidothioate
(3s):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3r 120 mg (yield: 87 %), a white solid. M.p.: 110-112℃. 1H
NMR (400 MHz, CDCl3): δ = 7.40-7.37 (m, 2H), 7.28-7.19 (m, 5H), 6.84-
6.79 (m, 2H), 3.74 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.6,
144.6, 134.2, 128.1, 128.0, 127.8, 127.3, 122.0, 55.5 ppm. HRMS (ESI)
m/z [M+H]+ Calcd for C14H13ClNOS2 (278.0401); found: 278.0408.
S-(2-bromophenyl) O-methyl phenylcarbonimidothioate (3m):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
compound 3m 152 mg (yield: 95 %), a white solid. M.p.: 78-80℃. 1H
NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 8.0 Hz, 1 H), 7.49 (d, J = 8.0 Hz,
1H), 7.25 (t, J = 8.0 Hz, 2H), 7.19-7.09 (m, 2H), 7.03 (t, J = 8.0 Hz, 1H),
6.91 (d, J = 8.0 Hz, 2H), 3.76 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 154.9, 146.1, 135.9, 132.3, 129.7, 129.5, 129.3, 128.0, 126.4, 123.0,
120.5,55.5 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C14H13BrNOS
(321.9896); found: 321.9891.
O-ethyl S-phenyl phenylcarbonimidothioate (3t): According to TP1,
the residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 15:1) to give the target compound 3s 114 mg (yield:
89 %), a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.38-7.36 (m, 2H),
7.24-7.18 (m, 5H), 6.99 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 8.0 Hz, 2H), 4.20
(q, J = 8.0 Hz, 2H), 1.06 (t, J = 8.0 Hz, 3H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 155.2, 146.2, 134.0, 128.1, 127.9, 127.7, 127.6, 122.7, 120.6,
64.0, 12.8 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C15H16NOS
(258.0947); found: 258.0955.
S-(4-nitrophenyl)
O-methyl
phenylcarbonimidothioate
(3n):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
1
compound 4f 94 mg (yield: 65 %), a white solid. M.p.: 94-96℃. H NMR
(400 MHz, CDCl3): δ = 8.06 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H),
7.25 (t, J = 8.0 Hz, 2H), 7.05 (t, J = 8.0 Hz, 1H), 6.86 (d, J = 8.0 Hz, 2H),
3.81 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 153.4, 146.7, 145.4,
136.8, 133.9, 128.1, 123.3, 122.6, 120.5, 55.8 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C14H13N2O3S (289.0642); found: 289.0647.
O-ethyl
S-phenyl (4-methoxyphenyl)carbonimidothioate (3u):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3t 136 mg (yield: 95 %), a colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.40-7.35 (m, 2H), 7.24-7.18 (m, 3H), 6.83-6.77 (m, 4H), 4.20
(q, J = 8.0 Hz, 2H), 3.69 (s, 3H), 1.06 (m, J = 8.0 Hz, 3H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 156.5, 156.3, 140.5, 135.1, 129.4, 128.7, 128.6,
122.7, 114.3, 65.0, 55.4, 13.9 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C16H18NO2S (288.1053); found: 288.1059.
S-(4-cyanophenyl)
O-methyl
phenylcarbonimidothioate
(3o):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
compound 3O 74 mg (yield: 56 %), a white solid. M.p.: 110-112℃. 1H
NMR (400 MHz, CDCl3): δ = 7.54-7.48 (m, 4H), 7.26 (t, J = 8.0 Hz, 2H),
7.06 (t, J = 8.0 Hz, 1H), 6.86 (d, J = 8.0 Hz, 2H), 3.81 (s, 3H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 153.7, 145.6, 134.6, 134.0, 131.1, 128.1,
123.4, 120.5, 117.2, 111.4, 55.7 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C15H13N2OS (269.0743); found: 269.0735.
O-ethyl S-phenyl (4-chlorophenyl)carbonimidothioate (3v): According
to TP1, the residue was purified by flash chromatography on silica gel
(petroleum ether/ethyl acetate = 20:1) to give the target compound 3u
134 mg (yield: 92 %), a colorless oil. 1H NMR (400 MHz, CDCl3): δ =
7.37-7.35 (m, 2H), 7.25-7.16 (m, 5H), 6.79 (d, J = 8.0 Hz, 2H), 4.18 (q, J
= 8.0 Hz, 2H), 1.06 (t, J = 8.0 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 155.9, 144.8, 134.1, 128.0, 127.9, 127.8, 127.7, 127.6, 122.0, 64.2,
12.8 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C15H15ClNOS (292.0558);
found: 292.0564.
O-methyl
S-(thiophen-2-yl)
phenylcarbonimidothioate
(3p):
According to TP1, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 20:1) to give the target
compound 3p 117 mg (yield: 94 %), a colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.35 (d, J = 4.0 Hz, 1H), 7.25 (t, J = 8.0 Hz, 2H), 7.06 (t, J =
4.0 Hz, 1H), 7.01 (t, J = 8.0 Hz, 1H), 6.90-6.86 (m, 3H), 3.25 (s, 3H) ppm.
13C NMR (100 MHz, CDCl3): δ = 155.2, 145.6, 135.6, 131.0, 128.0, 126.4,
124.8, 122.9, 120.6, 55.6 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C12H12NOS2 (250.0355); found: 250.0349.
O-ethyl S-phenyl (4-nitrophenyl)carbonimidothioate (3w): According
to TP1, the residue was purified by flash chromatography on silica gel
(petroleum ether/ethyl acetate = 10:1) to give the target compound 3v
125 mg (yield: 83 %), a primrose yellow solid. M.p.: 88-90℃. 1H NMR
(400 MHz, CDCl3): δ = 8.11 (d, J = 8.0 Hz, 2H), 7.39-7.36 (m, 2H), 7.30-
7.22 (m, 3H), 6.93 (d, J = 8.0 Hz, 2H), 4.23 (q, J = 8.0 Hz, 2H), 1.11 (t, J
= 8.0 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.5, 152.6, 142.9,
134.2, 128.3, 127.9, 126.8, 123.9, 121.2, 64.7, 12.8 ppm. HRMS (ESI)
m/z [M+H]+ Calcd for C15H15N2O3S (303.0798); found: 303.0806.
O,S-dimethyl phenylcarbonimidothioate (3q): According to TP1, the
residue was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate = 10:1) to give the target compound 3q 78 mg (yield:
86 %), a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.29 (t, J = 8.0 Hz,
2H), 7.07 (t, J = 8.0 Hz, 1H), 6.88 (d, J = 8.0 Hz, 2H), 3.96 (s, 3H), 2.32
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ = 157.9, 146.4, 127.9, 122.6,
120.5, 55.0, 12.5 ppm. HRMS (ESI) m/z [M+H]+ Calcd for C9H12NOS
(182.0634); found: 182.0642.
1,2-bis(O-methyl phenylcarbonimidothioate)disulfane (4a): According
to TP2, the residue was purified by flash chromatography on silica gel
(petroleum ether/ethyl acetate = 10:1) to give the target compound 4a 68
mg (yield: 82 %), a white solid. M.p.: 80-82℃. 1H NMR (400 MHz,
O-methyl S-phenyl (4-methoxyphenyl)carbonimidothioate (3r):
According to TP1, the residue was purified by flash chromatography on
CDCl3): δ = 7.22 (t, J = 8.0 Hz, 4H), 7.03 (t, J = 8.0 Hz, 2H), 6.82 (d, J =
8.0 Hz, 4H), 3.92 (m, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ = 153.4,
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10.1002/ejoc.201901884
European Journal of Organic Chemistry
FULL PAPER
144.9, 128.1, 123.3, 120.5, 56.2 ppm. HRMS (ESI) m/z [M+H]+ Calcd for
C18H21N2O2S2 (333.0726); found: 333.0732.
M. Botta, A. Trejos, R. K. Arvela, M. Larhed, M. Witvrouw, M. Michiels,
F.Christ, Z. Debyser, F. Corelli, J. Med. Chem. 2008, 51, 5125; e) B.
Mandal and B. Basu, RSC Adv. 2014, 4 , 13854-13881.
[2] a) A. G. M. Barrett, D. H. R. Barton, and R. Colle, J. Chem. Soc. 1980, 1.
1,2-bis(O-ethyl phenylcarbonimidothioate)disulfane (4b): According
to TP2, the residue was purified by flash chromatography on silica gel
(petroleum ether/ethyl acetate = 7:1) to give the target compound 4b 70
mg (yield: 78 %), a white solid. M.p.: 68-70℃. 1H NMR (400 MHz,
CDCl3): δ = 7.23 (t, J = 8.0 Hz, 4H), 7.03 (t, J = 8.0 Hz, 2H), 6.82 (d, J =
8.0 Hz, 4H), 4.34 (m, 4H), 1.36 (t, J = 8.0 Hz, 6H) ppm. 13C NMR (100
MHz, CDCl3): δ = 152.9, 145.2, 128.1, 123.2, 120.6, 64.9, 13.1 ppm.
HRMS (ESI) m/z [M+H]+ Calcd for C16H17N2O2S2 (361.1039); found:
361.1032.
665-671; b) L. Chen, T. R. Thompson, R. P. Hammer, B. George, J. Org.
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1,2-bis(O-ethyl (4-chlorophenyl)carbonimidothioate)disulfane (4c):
According to TP2, the residue was purified by flash chromatography on
silica gel (petroleum ether/ethyl acetate = 15:1) to give the target
[4] L. Zhang, H. Li, Q. Zhu, J. Liu, L. Chen, Y. Leng, H. L. Jiang, H. Liu,
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Y. Murata, S. Asano, R. Kato, Y. Kitamura, M. Matsumura, S.
1
compound 4c 80 mg (yield: 75 %), a white solid. M.p.: 62-64℃. H NMR
Yasuike, Catal. Commun. 2019, 132, 105808.
(400 MHz, CDCl3): δ = 7.18 (t, J = 8.0 Hz, 4H), 6.74 (t, J = 8.0 Hz, 4H),
4.32 (m, 4H), 1.33 (t, J = 8.0 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 153.2, 143.6, 128.6, 128.2, 121.9, 65.2, 13.1 ppm. HRMS (ESI) m/z
[M+H]+ Calcd for C18H19Cl2N2O2S2 (429.0260); found: 429.0265.
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5631.
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1,2-bis(O-(2,2,2-trifluoroethyl) phenylcarbonimidothioate)disulfane
(4d): According to TP2, the residue was purified by flash chromatography
on silica gel (petroleum ether/ethyl acetate = 10:1) to give the target
compound 4d 102 mg (yield: 87 %), a white solid. M.p.: 92-94℃. 1H NMR
(400 MHz, CDCl3): δ = 7.33 (t, J = 8.0 Hz, 4H), 7.15 (t, J = 8.0 Hz, 2H),
6.88 (d, J = 8.0 Hz, 4H), 4.70 (m, 4H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 150.9, 143.5, 128.3, 124.0, 121.9 (q, JC-F = 276 Hz), 120.1, 64.1 (q,
JC-F = 36.0 Hz) ppm. HRMS (ESI) m/z [M+H]+ Calcd for C18H15F6N2O2S2
(469.0474); found: 469.4078.
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Acknowledgments
[12] M. Y. Gao, J. H. Li, S. B. Zhang, L. J. Chen, Y. S. Li, Z. B. Dong, J. Org.
Chem. 2019, DOI: 10.1021/acs.joc.9b02543.
The financial support from Hubei Key Laboratory of Radiation
Chemistry and Functional Materials, Hubei University of Science
[13] a) X. Liu, Z. B. Dong, J. Org. Chem. 2019, 84, 11524-11532; b) Z. B.
Dong, M. Balkenhohl, E. Tan, P. Knochel, Org. Lett. 2018, 20, 7581-
7584; c) S. B. Zhang, X. Liu, M. Y. Gao, Z. B. Dong, J. Org. Chem.
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&
Technology (2019-20KZ01), Ministry-of-Education Key
Laboratory for the Synthesis and Application of Organic
Functional Molecules, Hubei University (KLSAOFM1810), Hubei
Provincial Science and Technology (2019CFB596), Key
Laboratory of Hubei Province for Coal Conversion and New
Carbon Materials (WKDM202003) are all greatly appreciated. K.
P. thanks the support of Postgraduate Innovation Foundation
from Wuhan Institute of Technology (CX2019171).
Keywords: C-S bond
•
S-S bond
•
Copper
•
Phenylcarbamothioate • Synthesis
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Key Topic*
Author(s), Corresponding Author(s)*
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Title
((Insert TOC Graphic here: max.
width: 5.5 cm; max. height: 5.0 cm;
NOTE: the final letter height should
not be less than 2 mm.))
*one or two words that highlight the emphasis of the paper or the field of the study
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Key Topic*: C-S/S-S Formation
Kang Peng, Ming-Yuan Gao, Yu-Yan Yi,
Jia Guo, and Zhi-Bing Dong *
Page No. – Page No.
Copper/Nickel-Catalyzed Selective C-
S/S-S Bond Formations Starting from
O-alkyl Phenylcarbamothioates
Text for Table of Contents (about 350 characters)
*one or two words that highlight the emphasis of the paper or the field of the study
A convenient and effective method is described to construct C-S/S-S bond starting from O-alkyl phenylcarbamothioates,
giving diverse O-alkyl S-phenyl phenylcarbonimidothioates and isothiourea disulfides, respectively. The C-S bond formation
products (O-alkyl S-phenyl phenylcarbonimidothioates) were synthesized by using Cu2O as catalyst in water (without phase
transfer catalyst), and the S-S bond formation product (isothiourea disulfides) could be furnished catalyzed by NiBr2 at room
temperature. These transformations feature easy control, environmental friendliness and good to excellent yields, which could
be attractive in the selective C-S/S-S bond formation.
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