I2/PhI(OAc)2 Copromoted Amination Reaction: Synthesis of α-Dicarbonylsulfoximine Derivatives by Incorporating an Intact Dimethyl Sulfoxide

Article abstract of DOI:10.1021/acs.joc.9b01160

An I₂/PhI(OAc)₂ copromoted strategy using dimethyl sulfoxide as an "S/C2/O" source for preparing α-dicarbonylsulfoximine derivatives is reported. This process involves oxidative coupling to construct a C-N bond and electrophilic amin

Full text of DOI:10.1021/acs.joc.9b01160

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Note
I2/PhI(OAc)2 co-promoted Amination Reaction:
Synthesis of #-dicarbonylsulfoximine Derivatives
by Incorporating an Intact Dimethyl Sulfoxide
Peng Zhao, Xia Wu, Xiao Geng, Can Wang, You Zhou, Yan-Dong Wu, and An-Xin Wu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01160 • Publication Date (Web): 29 May 2019
Downloaded from http://pubs.acs.org on May 29, 2019
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I2/PhI(OAc)2 co-promoted Amination Reaction: Synthesis of
α-dicarbonylsulfoximine Derivatives by Incorporating an
Intact Dimethyl Sulfoxide
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Peng Zhao+, Xia Wu+, Xiao Geng, Can Wang, You Zhou, Yan-Dong Wu, and
An-Xin Wu*†
†Key Laboratory of Pesticide & Chemical Biology, Ministry of Education,
College of Chemistry, Central China Normal University, Wuhan 430079, P. R.
China
*E-mail: chwuax@mail.ccnu.edu.cn.
TOC Graphic:
O
O
S
O
CH3
O
I2, PhI(OAc)2
130 oC
N
N
H4HCO3
+
+
S
Ar
H3C
CH3
Ar
H3C
O
DMSO serves as substrates, oxidant
N as bridge to construct -dicarbonylsulfoximines
electrophilic amination was used to build N=S bond
Simple conditions
Abstract: An I2/PhI(OAc)2 co-promoted strategy using dimethyl sulfoxide as a
“S/C2/O” source for preparing α-dicarbonylsulfoximine derivatives is reported.
This process involves oxidative coupling to construct a C–N bond and
electrophilic amination of dimethyl sulfoxide to afford an N=S bond, with
dimethyl sulfoxide presents in the final product as an intact molecule.
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Furthermore, tetramethylene sulfoxide as a solvent is also well compatible with
this amination reaction.
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9
Dimethyl sulfoxide (DMSO) is an important polar aprotic solvent and mild
oxidant, as well as building block that has been widely used in synthesis of
organic compounds and pharmaceuticals owing to its low cost and
eco-benign properties.1,2 In past decades, numerous methods have been
developed using DMSO as a versatile reagent. For example, DMSO has been
used as: (i) an one carbon (C1) synthon to achieve methylation, formylation,
cyanation etc.;3 (ii) a “S/C1” source to introduce methylthio (MeS) group;4
(iii) a “S/C2” source by providing an electrophilic “–CH2SCH3” unit;5 (iv) a
source of “oxygen” or an oxidant;6 (v) a “S/C1/O” source to insert a “-SOMe”
group into the target molecule. 7 In contrast, DMSO has rarely been used as
a “S/C2/O” source,8,9 presumably due to activated DMSO being prone to
C–S or S–O bond cleavage. In 2018, Wang and co-workers reported an
elegant method dividing DMSO into two fragments for addition to the
target compound (Scheme 1a).8 Recently, Cai’s group reported an efficient
visible light-enabled method for convenient incorporation of an intact
DMSO molecule into the target product (Scheme 1b).9 Despite these
fulfilling methods discovered in recent years, there is still a demand for the
development of DMSO as a “S/C2/O” source, especially incorporation of an
intact DMSO molecule into the target product.
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Scheme 1. Application of DMSO as “S/C2/O” source.
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Wang's work:
Ar
Ar
N
O
O
S
CH3
hv (365-370 nm)
S
N
N
a
+
FeSO4 7H2O
H3C
N
Ar
O
H3C
CH3
Ar
H2O2
7
8
9
Cai's work:
R3
4CzIPN, PIFA
1,3,5-trimethoxybenzene
O
S
O
O
S
Ar1
+
H3C
C
b
c
HO
Ar1
H2
R3 Ar2
blue LEDs
H3C
CH3
Ar2
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This work
:
O
O
O
CH3
O
I2/Ph(OAc)2
N
S
H3C
N
H4HCO3
+
+
S
Ar
H3C
CH3
Ar
O
Sulfoximines are important structural motifs because they are widely found
in diverse natural products, pharmaceuticals and agrochemicals.10, 11 In past
decades, many notable advances toward the synthesis of sulfoximine
derivatives have been reported,12 such as the seminal contribution of Bolm et
al.13 However, developing a concise and efficient synthetic approach to
sulfoximines remains highly attractive. Herein, we first reported an I2/PhI(OAc)2
co-promoted protocol to access α-dicarbonylsulfoximines from methyl
ketone, ammonium bicarbonate and DMSO. Moreover, TMSO (tetramethylene
sulfoxide) was also well compatible with this amination reaction to various
cyclic sulfoximines. It should be noted that this method can achieve amination
of
sulfoxide
to
in-situ
forge
S,S-dimethyl
sulfoximine
or
S,S-tetramethylenesulfoximide, which avoid high cost of commercial purchase
and cumbersome pre-preparation (Scheme 1c).
As we continue to focus on the synthesis of various nitrogen-containing
compounds,14 we initial explore the acetophenone 1a, ammonium
bicarbonate 2a and DMSO reacting at 80 °C afforded the
α-dicarbonylsulfoximine 4a albeit in trace yield (Table 1, entry 1).
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Subsequently, we further tested the reaction in the temperature range of 100
°C to 130 °C, and the results showed that 130 °C was the best for the reaction
(Table 1, entries 2−4). Subsquently, different amounts of PIDA and ammonia
bicarbonate were screened. The best results were seen with 2.5 mmol of PIDA
and 3.0 equiv of ammonia bicarbonate (Table 1, entries 5−9 , Table S1,
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Table 1. Optimization of the Reaction Conditionsa
O
O
N
O
S
I2, PhI(OAc)2
temp
S
N
H4HCO3
+
+
O
O
1a
3a
4a
2a
entry
Temp
(°C)
80
PhI(OAc)2
(mmol)
2.5
I2
yield[b]
(%)
trace
63
(equiv)
1.6
1
2
3
4
5
6
7
8
100
120
130
130
130
130
130
2.5
1.6
2.5
1.6
68
2.5
1.6
71
0.5
1.6
trace
5
1.0
1.6
2.0
1.6
40
2.75
1.6
70
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130
3.0
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
1.6
68
0
10
11
12
13
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16c
17d
130
130
130
130
130
130
130
130
−
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0.1
0.3
0.5
1.0
2.0
0.5
0.5
8
58
71
70
68
0
0
aReaction conditions: 1a (0.5 mmol), 2a (1.5 mmol), I2 and PhI(OAc)2 heated in 4 mL of DMSO.
bProducts were obtained in isolated yields. IBX was used instead of PIDA. PIFA was used
instead of PIDA.
c
d
entries 5−8 ). Moreover, the amount of I2 was optimized and the reaction
proceed smoothly even with a small amount of 0.5 equiv (Table 1, entries
10−15). However, without adding I2, the reaction did not occur (Table 1, entry
10). Next, a series of ammonia sources (NH4Cl, NH4OAc, NH2CO2NH4,
HCOONH4, (NH4)2CO3, and (NH4)2C2O4H2O) were screened for the reaction,
and NH4HCO3 was found to give the best result (Table S1, entries 20−25).
Finally, 2-iodoxybenzoic acid (IBX) and phenyliodine bis(trifluoroacetate)
(PIFA) were used as hypervalent iodine reagents instead of PIDA to promote
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this reaction. However, no product was obtained in these cases (Table 1,
6
7
8
entries 16−17).
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The generality of the new electrophilic amination reaction was explored
under the optimized conditions (Scheme 2). The electron-donating (Me, OMe,
3,4-OCH2O), halogen, (F, Cl, Br, I) and electron-deficient (CH3SO2, COOMe, Ph)
groups on the aryl rings showed excellent reactivities for this amination
reaction
(4a−4p,
78%−40%).
Furthermore,
sterically
hindered
1-acetonaphthone and 2-acetonaphthone were well compatible with this
amination reaction (4q−4r, 78%−77%). Moreover, heteroaryl ketones, such as
thiophenyl, benzofuryl methyl ketones as well as those with different
substituents groups attached to thiophene ring could be readily applied to the
α-dicarbonylsulfoximines scaffold (4s−4w, 76%−42%).
Scheme 2. Scope of the amination Reactionab
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O
O
O
S
I2, PhI(OAc)2
N
S
N
+
H4HCO3
+
R
O
R
130 o
C
O
4
1
2a
3a
O
O
O
N
N
N
S
S
S
S
S
S
S
O
O
O
O
O
O
O
O
O
O
O
O
4a
4b
4c
71%
73%
78%
O
OMe O
O
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N
N
N
MeO
O
S
S
O
68%
O
O
54%
O
4d
4e
4f
45%
O
O
O
N
N
N
O
O
O
Cl
Br
Cl
Cl
Cl
4i
O
4g
4h
72%
74%
60%
Cl
O
O
N
N
O
N
O
S
S
S
S
S
S
O
O
O
O
O
O
Br
4k
O
I
4j
4l
O
69%
50%
65%
O
N
N
N
O
O
O
54%
O
O
48%
F
S
MeOOC
4m
4n
4o
62%
O
O
O
O
N
N
N
S
S
S
S
S
S
O
O
O
O
O
O
78%
O
40%
O
Ph
4p
O
4q
O
4r
O
77%
N
N
N
O
O
O
O
60%
S
O
58%
O
76%
S
4s
4t
4u
O
O
N
N
S
S
O
S
O
O
S
Br
4v
4w
42%
51%
aReaction conditions: 1 (0.5 mmol), 2a (1.5 mmol), I2 (0.25 mmol) and PhI(OAc)2 (2.5 mmol)
b
heated in 4 mL of DMSO at 130 °C in a pressure vessel for 1 h. Products were obtained in
isolated yields.
Next, we have also studied various sulfoxide compounds under optimal
conditions, such as tetramethylene sulfoxide, tert-Butyl methyl sulphoxide,
methyl phenyl sulfoxide, benzyl sulfoxide. Fortunately, tetramethylene
sulfoxide (TMSO) was well compatible with this amination reaction to obtain
product 5a in 48% yield. Subsequently, we have also explored the
compatibility of the substrate with TMSO as the solvent under standard
conditions (Scheme 3). Substituted by an electron-donating group (Me, OMe),
halogen-substituted (F, Cl, Br) acetophenone were well compatible with this
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amination reaction, affording the desired products in moderate yields (5b−5h,
60%−42%). Electron-deficient (COOMe) group substituted acetophenone was
compatible with this amination reaction under standard conditions to give the
desired product 5i in 32% yield. Notably, naphthylketone with higher steric
hindrance reacted smoothly with TMSO as the solvent under standard
conditions (5j−5k, 65%−62%). Finally, methyl ketones containing thiophenyl
moieties could tolerance in optimized conditions, affording 5l in 50% yield.
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Scheme 3. Scope of the amination Reaction in Tetramethylene sulfoxide ab
O
O
O
S
N
I2, PhI(OAc)2
130 o
N
H4HCO3
+
+
R
S
R
O
C
O
5
1
2a
3b
O
O
O
O
O
O
O
S
N
S
S
N
N
O
O
O
5a
48%
O
5b
5c
56%
O
45%
O
O
O
O
O
S
S
S
N
N
N
O
O
O
F
Cl
5d
5e
OMe
54%
O
42%
O
5f
52%
O
O
S
S
S
N
N
N
O
O
O
Cl
Br
MeOOC
Cl
5g
5h
5i
60%
49%
32%
O
O
O
O
O
O
S
S
S
N
N
N
O
O
O
S
5j
5k
5l
62%
65%
50%
aReaction conditions: 1 (0.5 mmol), 2a (1.5 mmol), I2 (0.25 mmol) and PhI(OAc)2 (2.5 mmol)
b
heated in 2 mL of tetramethylene sulfoxide at 130 °C in a pressure vessel for 1 h. Products
were obtained in isolated yields.
We have carried out several control experiments to explore mechanism of
the reaction (Scheme 4). Acetophenone (1a, 0.5 mmol) reaction under optimal
conditions could afford phenylglyoxal 1ab and the corresponding hydrated
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species 1ac (Scheme 4a). α-Iodoketone 1aa was reacted with ammonium
bicarbonate 2a in DMSO under the standard conditions, giving the desired
product 4a in 43% (Scheme 4b). However, when the hydrated species 1ac was
used as substrate, 4a was not obtained (Scheme 4c). α-Iodoketone 1aa and
the hydrated species 1ac were reacted with S,S-dimethyl sulfoximine 7a under
optimal conditions affording the α-dicarbonylsulfoximine 4a in 50% and 49%
yields. (Schemes 4d, 4e). The above results showed that α-Iodoketone 1aa and
phenylglyoxal 1ab were intermediates in this amination reaction and the
phenylglyoxal 1ab and 7a were formed concurrently. Finally, the reaction of a
prepared substrate 6a with DMSO was performed under the optimum
conditions, but 4a could not be obtained (Scheme 4f). These results clearly
excluded the possibility of α-ketoamide 6a being an intermediate, further
confirming that 7a generated in situ from ammonium bicarbonate and DMSO
(for details, see Supporting Information).
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Scheme 4. Control Experiments
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O
O
O
O
OH
I2, PhI(OAc)2
DMSO, 130 o
+ H2O
- H2O
a
C
OH
1ac
> 99% conversion
1a
1ab
O
O
N
O
S
I2, PhI(OAc)2
130 o
I
S
+
N
+
+
H4HCO3
b
O
Ph
Ph
O
C
1aa
2a
3a
4a
43%
O
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O
N
N
O
S
I2, PhI(OAc)2
130 o
OH
S
S
N
H4HCO3
c
+
O
O
O
C
OH
1ac
2a
3a
4a
0%
O
O
I2, PhI(OAc)2
130 o
HN
O
O
S
I
+
+
d
Ph
Ph
O
C
1aa
7a
4a
4a
50%
O
O
I2, PhI(OAc)2
130 o
N
N
OH
OH
HN
S
S
S
O
O
e
f
O
C
1ac
7a
49%
O
O
O
I2, PhI(OAc)2
130 o
NH2
S
Ph
+
O
C
O
6a
3a
4a
0%
Based on the aforementioned results and previous reports,15 a possible
mechanism was proposed (Scheme 5). Ammonium bicarbonate 2a was used
as source of ammonia through a decomposition reaction. Subsequently,
ammonia 2aa could react with PhI(OAc)2 (PIDA) to form intermediate A via
AcOH elimination. Next, amination of dimethyl sulfoxide to construct the N=S
bond can proceed via two pathways. In path a, iminoiodinanes intermediate A
could be trapped by a dimethyl sulfoxide molecule to produce S,S-dimethyl
sulfoximine 7a. In path b, A could combine with iodosobenzene (PhI=O) to
generate intermediate B. The latter could undergo electrophilic amination to
obtain C, which subsequently transforms into 7a. Concurrently, 1a is
converted to phenylglyoxal 1ab, releasing HI and dimethyl sulfide (DMS) via
sequential iodination/Kornblum oxidation. The S,S-dimethyl sulfoximine 7a
reacted with the aldehyde group of phenylglyoxal 1ab to give intermediate
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4aa via in situ cross-trapping and subsequent rapidly oxidation to obtained
the desired product 4a in presence of I2.
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Scheme 5. Proposed Mechanism
PhI(OAc)2
H2O
2 AcOH
path b
PhI(OAc)2
PhI
O
H+
I
I
N
H4HCO3
N
H3
I
Ph
NH
I
NH
Ph
Ph
N
N
Ph
2a
2aa
A
B
2 AcOH
H2O + PhI
O
path a
O
S
S
PhI
2 AcOH
N
C
O
S
NH
O
S
+
I
Ph
7a
PhI(OAc)2
O
O
I2
O
I2
O
O
O
S
N
O
I
N
Ph
S
Ph
Ph
Ph
Ph
S
O
O
2 HI
O
4a
HI + DMS
1a
HI
1ab
4aa
1aa
OH
Conclusion
In summary, we present a I2/PhI(OAc)2 co-promoted approach to accessing
α-dicarbonylsulfoximines from methyl ketone, ammonium bicarbonate, and
dimethyl sulfoxide. The reaction proceeds via oxidative coupling to construct a
C–N bond and electrophilic amination to form an N=S bond. Notably, DMSO
acts simultaneously as a solvent, oxidant, and substrate in this transformation.
Moreover, TMSO is also well compatible with this reaction as a solvent. This
protocol is an efficient method for enriching the scope of DMSO as a
multipurpose fragment by incorporating DMSO into the final product as an
intact molecule. Further studies aimed at elucidating the detailed reaction
mechanism and exploiting this I2/PhI(OAc)2 co-promoted strategy are
underway in our laboratory.
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Experimental Section
General Methods.
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Unless otherwise stated, all starting materials and catalysts were obtained
from commercial suppliers and used without further purification. All new
compounds were fully characterized. TLC analysis was performed using
pre-coated glass plates. Column chromatography was performed using silica
gel (200–300 mesh). IR spectra were recorded on a PerkinElmer PE-983
1
infrared spectrometer as KBr pellets with absorption in cm–1. H NMR spectra
were recorded in DMSO-d6 or CDCl3 on 300/400/600 MHz NMR spectrometers,
and resonances (δ) are given in parts per million relative to tetramethylsilane
(internal standard). Data are reported as follows: chemical shift, multiplicity (s
= singlet, d = doublet, t = triplet, m = multiplet, q = quadruple), coupling
constants (Hz), and integration. 13C spectra were recorded in DMSO-d6 or
CDCl3 on 75/100/150 MHz NMR spectrometers, and resonances (δ) are given
in ppm. HRMS were obtained on a Bruker 7-T FT-ICR MS equipped with an
electrospray source. The X-ray crystal structure determinations of 4a was
obtained on a Bruker SMART APEX CCD system. Melting points were
determined using an XT-4 apparatus and not corrected.
Caution! NI3 can be generated even at room temperature, and it is an
extremely dangerous molecule. Therefore we suggest proper protection at all
scales. The temperature of the water bath of the rotary evaporator was 35 °C.
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General Procedures for the Synthesis of Products 4 (4a as an example).
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A mixture of acetophenone 1a (0.5 mmol), 2a (1.5 mmol), PhI(OAc)2 (2.5
mmol) and iodine (0.25 mmol) in DMSO (4 mL), the mixture was stirred at 130
°C (oil bath) for 1 h. Then the mixture was quenched with saturation Na2S2O3
solution (50 mL), extracted with EtOAc (3 × 50 mL). The combined organic
layers were washed with brine, dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude product was purified by
column chromatography on silica gel (eluent: petroleum ether/EtOAc = 2/1)
to afford the product 4a.
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General Procedures for the Synthesis of Products 5(5a as an example).
A mixture of acetophenone 1a (0.5 mmol), 2a (1.5 mmol), PhI(OAc)2 (2.5
mmol) and iodine (0.25 mmol) in TMSO (2 mL), the mixture was stirred at 130
°C (oil bath) for 1 h. Then the mixture was quenched with saturation Na2S2O3
solution (50 mL), extracted with EtOAc (3 × 50 mL). The combined organic
layers were washed with brine, dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude product was purified by
column chromatography on silica gel (eluent: petroleum ether/EtOAc = 2/1)
to afford the product 5a.
General Procedures for the Synthesis of α-Iodoketone 1aa
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Acetophenone (1.2 g) and I2 (2.79 g), CuO (875 mg) heat in methanol at 65 °C
(oil bath) till almost completed conversion of the substrates by TLC analysis.
The reaction solution was then quenched with 80 mL of saturated sodium
thiosulfate solution and extracted with ethyl acetate (3 × 50 mL). The
combined organic layers were washed with brine, dried over anhydrous
Na2SO4 and concentrated under reduced pressure to afford the α-Iodoketone
1aa as a brown oil in 95% yield.
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General Procedures for the Synthesis of α-ketoamide 6a
The reaction of acetophenone (600 mg), formamidine hydrochloride (400
mg) with I2 (1.01 g) in DMSO at 110 °C (oil bath) for 11 h. The reaction mixture
washed with saturated sodium thiosulfate solution and extracted with ethyl
acetate (3 × 50 mL). The combined organic layer dried over Na2SO4 and
concentrated in vacuo. The crude product was purified by column
chromatography on silica gel (eluent: petroleum ether/EtOAc = 5/1) to afford
the 6a. 1H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.6 Hz,
1H), 7.47 (t, J = 7.6 Hz, 2H), 7.10 (s, 1H), 6.58 (s, 1H).
Analytical Data for Products 4a-5l
N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxo-2-phenylacetamid
e (4a): Prepare according to the description in the general experimental
procedure. Yield 71%; 160 mg; yellow solid; mp 73−75 °C; IR (KBr): 1680, 1626,
1
1348, 1225, 1046 cm-1, H NMR (600 MHz, CDCl3): δ 8.04 (d, J = 7.8 Hz, 2H),
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7.62 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 3.46 (s, 6H); C{1H} NMR (150
MHz, CDCl3) δ 190.2, 173.2, 134.3, 132.6, 130.1, 128.7, 42.1; HRMS (ESI): m/z
[M + H]+ calcd for C10H12NO3S: 226.0532; found: 226.0530.
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N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxo-2-(p-tolyl)acetamide
(4b):
Prepare according to the description in the general experimental procedure.
Yield 73%; 174.7 mg; yellow solid; mp 119−121 °C; IR (KBr): 1672, 1626, 1350,
1
1426, 1201, 1045, 810 cm-1; H NMR (600 MHz, CDCl3): δ 7.93 (d, J = 8.0 Hz,
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2H), 7.28 (d, J =9.0 Hz, 2H), 3.45 (s, 6H), 2.42 (s, 3H); C{1H} NMR (150 MHz,
CDCl3) δ 214.5, 189.9, 173.4, 145.4, 130.2, 129.4, 42.1, 21.8; HRMS (ESI): m/z [M
+ H]+ calcd for C11H14NO3S: 240.0689; found: 240.0683.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxo-2-(o-tolyl)acetamide
(4c):
Prepare according to the description in the general experimental procedure.
Yield 78%; 186.6 mg; yellow solid; mp 164−166 °C; IR (KBr): 1680, 1626, 1504,
1440, 1239, 1192, 1124, 1076, 772 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.79 (d, J
= 8.1 Hz, 1H), 7.49−7.40 (m, 1H), 7.33−7.24 (m, 2H), 3.43 (s, 6H), 2.61 (s, 3H);
13C{1H} NMR (75 MHz, CDCl3) δ 192.6, 173.7, 140.9, 133.0, 132.3, 132.1, 131.7,
125.7, 42.0, 21.5; HRMS (ESI): m/z [M + H]+ calcd for C11H14NO3S: 240.0689;
found: 240.0683.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(3-methoxyphenyl)-2-oxoacetami
de (4d): Prepare according to the description in the general experimental
procedure. Yield 68%; 173.6 mg; yellow solid; mp 74−76 °C; IR (KBr): 1686,
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1619, 1259, 1510, 1426, 1254, 1224, 1196, 1168, 1081 cm-1; 1H NMR (300 MHz,
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CDCl3): δ 7.61 (d, J = 7.8 Hz, 1H), 7.58−7.53 (m, 1H), 7.44−7.35 (m, 1H),
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7.20−7.13 (m, 1H), 3.86 (s, 3H), 3.45 (s, 6H); C{1H} NMR (75 MHz, CDCl3) δ
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190.0, 173.1, 159.8, 133.9, 129.7, 123.3, 121.2, 113.3, 55.4, 42.1; HRMS (ESI):
m/z [M + H]+ calcd for C11H14NO4S: 256.0638; found: 256.0635.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(2-methoxyphenyl)-2-oxoacetami
de (4e): Prepare according to the description in the general experimental
procedure. Yield 45%; 114.9 mg; yellow solid; mp 95−97 °C; IR (KBr): 1684,
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1633, 1287, 1215, 1149, 1033, 1008 cm-1; H NMR (300 MHz, CDCl3): δ
7.90−7.82 (m, 1H), 7.60−7.50 (m, 1H), 7.10−6.93 (m, 2H), 3.88 (s, 3H), 3.41 (s,
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6H); C{1H} NMR (75 MHz, CDCl3) δ 190.2, 173.9, 160.1, 135.6, 130.8, 123.2,
121.0, 112.0, 55.8, 41.9; HRMS (ESI): m/z [M + H]+ calcd for C11H14NO4S:
256.0638; found: 256.0635.
2-(benzo[d][1,3]dioxol-5-yl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoa
cetamide (4f): Prepare according to the description in the general
experimental procedure. Yield 54%; 154.4 mg; yellow solid; mp 126−128 °C; IR
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(KBr): 1668, 1611, 1375, 1266, 1227, 1096, 1028 cm-1; H NMR (600 MHz,
CDCl3): δ 7.69−7.63 (m, 1H), 7.50 (s, 1H), 6.87 (d, J = 8.4 Hz, 1H), 6.07 (s, 2H),
3.45 (s, 6H); 13C{1H} (150 MHz, CDCl3) δ 188.4, 173.4, 152.9, 148.2, 127.7, 127.3,
108.9, 108.2, 102.0, 42.1; HRMS (ESI): m/z [M + H]+ calcd for C11H12NO5S:
270.0431; found: 270.0430.
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2-(4-chlorophenyl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoacetamide
(4g): Prepare according to the description in the general experimental
procedure. Yield 72%; 187.0 mg; yellow solid; mp 130−132 °C; IR (KBr): 1681,
1608, 1587, 1217, 1199, 1032, 816 cm-1; 1H NMR (600 MHz, CDCl3): δ 7.99 (d, J
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= 7.8 Hz, 2H), 7.46 (d, J = 7.8 Hz, 2H), 3.46 (s, 6H); C{1H} NMR (150 MHz,
CDCl3) δ 188.8, 172.5, 140.8, 131.4, 131.1, 129.0, 42.1; HRMS (ESI): m/z [M +
H]+ calcd for C10H11ClNO3S: 260.0143; found: 260.0140.
2-(3,4-dichlorophenyl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoaceta
mide (4h): Prepare according to the description in the general experimental
procedure. Yield 74%; 217.7 mg; yellow solid; mp 96−98 °C; IR (KBr): 1690,
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1612, 1581, 1347, 1219, 1201, 1045 cm-1; H NMR (600 MHz, CDCl3): δ
8.17−8.11 (m, 1H), 7.92−7.85 (m, 1H), 7.57 (d, J = 8.4 Hz, 1H), 3.47 (s, 6H);
13C{1H} (150 MHz, CDCl3) δ 187.5, 171.6, 138.9, 133.3, 132.4, 131.7, 130.8,
129.1, 42.0; HRMS (ESI): m/z [M + H]+ calcd for C10H10Cl2NO3S: 293.9753;
found: 293.9752.
2-(2,4-dichlorophenyl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoaceta
mide (4i): Prepare according to the description in the general experimental
procedure. Yield 60%; 176.4 mg; yellow solid; mp 111−113 °C; IR (KBr): 1639,
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1212 cm-1; H NMR (600 MHz, CDCl3): δ 7.71 (d, J = 8.4 Hz, 1H), 7.45 (s, 1H),
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7.37 (d, J= 7.8 Hz, 1H), 3.43 (s, 6H); C{1H} (150 MHz, CDCl3) δ 189.3, 170.8,
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139.3, 134.2, 132.60, 132.6, 130.2, 127.5, 41.5; HRMS (ESI): m/z [M + H]+ calcd
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for C10H10Cl2NO3S: 293.9753; found: 293.9751.
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2-(4-bromophenyl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoacetamid
e (4j): Prepare according to the description in the general experimental
procedure. Yield 69%; 209.8 mg; yellow solid; mp 142−144 °C; IR (KBr): 1682,
1608, 1585, 1335, 1215, 1120, 1032 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.91 (d,
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J = 8.4 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 3.46 (s, 6H); C{1H} NMR (75 MHz,
CDCl3) δ 189.0, 172.4, 132.0, 131.49, 131.45, 129.7, 42.1; HRMS (ESI): m/z [M +
H]+ calcd for C10H11BrNO3S: 303.9638; found: 303.9634.
2-(2-bromophenyl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoacetamid
e (4k): Prepare according to the description in the general experimental
procedure. Yield 50%; 152 mg; yellow oil; IR (KBr): 1696, 1629, 1586, 1337,
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1305, 1260, 1212, 1029 cm-1; H NMR (600 MHz, CDCl3): δ 7.58 (d, J = 7.2 Hz,
1H), 7.53 (d, J = 7.8 Hz, 1H), 7.37−7.28 (m, 2H), 3.35 (s, 6H); 13C{1H} NMR (150
MHz, CDCl3) δ 191.2, 170.3, 136.6, 133.3, 133.2, 131.6, 127.5, 120.0, 41.4; HRMS
(ESI): m/z [M + H]+ calcd for C10H11BrNO3S: 303.9638; found: 303.9632.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(2-iodophenyl)-2-oxoacetamide
(4l): Prepare according to the description in the general experimental
procedure. Yield 65%; 228.1 mg; yellow oil; IR (KBr): 1694, 1626, 1260, 1211,
1057, 1039 cm-1; 1H NMR (600 MHz, CDCl3): δ 7.92 (d, J = 7.8 Hz, 1H), 7.60 (d, J
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= 7.2 Hz, 1H), 7.45 (s, 1H), 7.20 (s, 1H), 3.44 (s, 6H); C{1H} NMR (150 MHz,
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CDCl3) δ 191.8, 169.7, 140.3, 139.4, 133.0, 131.6, 128.0, 92.7, 41.6; HRMS (ESI):
m/z [M + H]+ calcd for C10H11INO3S: 351.9499; found: 351.9492.
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N-(dimethyl(oxo)-6-sulfaneylidene)-2-(4-fluorophenyl)-2-oxoacetamide
(4m): Prepare according to the description in the general experimental
procedure. Yield 54%; 131 mg; yellow solid; mp 115−117 °C; IR (KBr): 1683,
1622, 1596, 1346, 1212, 1104 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.13−8.05 (m,
2H), 7.16 (t, J = 8.7 Hz, 2H), 3.46 (s, 6H); 13C{1H} NMR (75 MHz, CDCl3) δ 188.5,
172.7, 168.1, 164.7, 133.0, 132.8, 129.12, 129.08, 116.1, 115.8, 42.1; HRMS (ESI):
m/z [M + H]+ calcd for C10H11FNO3S: 244.0438; found: 244.0435.
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N-(dimethyl(oxo)-6-sulfaneylidene)-2-(4-(methylsulfonyl)phenyl)-2-oxo
acetamide (4n): Prepare according to the description in the general
experimental procedure. Yield 62%; 187.9 mg; yellow oil; IR (KBr): 1684, 1633,
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1287, 1215, 1149, 1033, 1008, 779 cm-1; H NMR (600 MHz, DMSO-d6): δ
8.22−8.11 (m, 4H), 3.60 (s, 6H), 3.33 (s, 3H); 13C{1H} NMR (150 MHz, DMSO-d6)
δ 189.7, 171.5, 145.3, 136.1, 130.4, 127.8, 43.16, 41.17; HRMS (ESI): m/z [M +
H]+ calcd for C11H14NO5S2: 304.0308; found: 304.0302.
methyl
4-(2-((dimethyl(oxo)-6-sulfaneylidene)amino)-2-oxoacetyl)benzoate
(4o): Prepare according to the description in the general experimental
procedure. Yield 48%; 135.8 mg; yellow solid; mp 119−121 °C; IR (KBr): 1717,
1684, 1608, 1346, 1283, 1216, 1032, 821cm-1; 1H NMR (600 MHz, CDCl3) δ 8.12
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(d, J = 10.2 Hz, 4H), 3.95 (s, 3H), 3.48 (s, 6H); 13C{1H} NMR (150 MHz, CDCl3) δ
189.3, 172.3, 166.0, 135.9, 134.6, 130.0, 129.7, 52.5, 42.1; HRMS (ESI): m/z [M +
H]+ calcd for C12H14NO5S: 284.0587; found: 284.0585.
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2-([1,1'-biphenyl]-4-yl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoaceta
mide (4p): Prepare according to the description in the general experimental
procedure. Yield 40%; 120.4 mg; yellow solid; mp 135−137 °C; IR (KBr): 1685,
1656, 1509, 1460, 1446, 1248, 1220, 1203, 761 cm-1; 1H NMR (300 MHz, CDCl3):
δ 8.11 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 8.4Hz, 2H), 7.62 (d, J = 6.9Hz, 2H),
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7.52−7.39 (m, 3H), 3.47 (s, 6H); C{1H} NMR (75 MHz, CDCl3) δ 189.8, 173.1,
146.9, 139.6, 131.3, 130.67, 128.9, 128.4, 127.3, 42.1; HRMS (ESI): m/z [M + H]+
calcd for C16H16NO3S: 302.0845; found: 302.0842.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(naphthalen-2-yl)-2-oxoacetamid
e (4q): Prepare according to the description in the general experimental
procedure. Yield 77%; 212.0 mg; yellow solid; mp 141−143 °C; IR (KBr): 1679,
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1606, 1331, 1309, 1255, 1232, 1170, 1043, 1020, 817 cm-1; H NMR (300 MHz,
CDCl3): δ 8.60 (s, 1H), 8.10−8.02 (m, 1H), 8.00−7.83 (m, 3H), 7.66−7.51 (m, 2H),
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3.48 (s, 6H); C{1H} NMR (75 MHz, CDCl3) δ 192.8, 173.6, 134.9, 133.8, 133.6,
131.0, 128.7, 128.60, 128.57, 126.63, 125.59, 124.3, 41.9; HRMS (ESI): m/z [M +
H]+ calcd for C14H14NO3S: 276.0689; found: 276.0685.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(naphthalen-1-yl)-2-oxoacetamid
e (4r): Prepare according to the description in the general experimental
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procedure. Yield 78%; 214.7 mg; yellow solid; mp 93−95 °C; IR (KBr): 1670,
1606, 1224, 1201, 1176, 1097, 1026 cm-1; 1H NMR (300 MHz, CDCl3): δ 9.00 (d,
J = 8.7 Hz, 1H), 8.13−8.01 (m, 2H), 7.87 (d, J = 8.1 Hz, 1H), 7.68−7.47 (m, 3H),
3.41 (s, 6H); 13C{1H} NMR (75 MHz, CDCl3) δ 192.8, 173.6, 134.9, 133.8, 133.6,
131.0, 128.7, 128.6, 128.6, 126.6, 125.6, 124.3, 41.9; HRMS (ESI): m/z [M + H]+
calcd for C14H14NO3S: 276.0689; found: 276.0683.
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2-(benzofuran-2-yl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoacetamid
e (4s): Prepare according to the description in the general experimental
procedure. Yield 60%; 159.2 mg; yellow solid; mp 126−128 °C; IR (KBr): 1669,
1
1639, 1540, 1347, 1310, 1265, 1213, 1134, 1037 cm-1; H NMR (300 MHz,
CDCl3): δ 8.07−8.04 (m, 1H), 7.73−7.69 (m, 1H), 7.61−7.46 (m, 2H), 7.34−7.27
(m, 1H), 3.51 (s, 6H); 13C{1H} NMR (75 MHz, CDCl3) δ 178.0, 169.5, 156.2, 149.6,
129.3, 126.9, 124.0, 123.89, 120.2, 112.4, 41.7; HRMS (ESI): m/z [M + H]+ calcd
for C12H12NO4S: 266.0482; found: 266.0487.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxo-2-(thiophen-2-yl)acetamide
(4t): Prepare according to the description in the general experimental
procedure. Yield 58%; 134.0 mg; yellow solid; mp 87−89 °C; IR (KBr): 1641,
1
1603, 1408, 1237, 1217, 1057, 1034 cm-1; H NMR (300 MHz, CDCl3): δ
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8.14−8.01 (m, 1H), 7.80−7.73 (m, 1H), 7.20−7.12 (m, 1H), 3.47 (s, 6H); C{1H}
NMR (75 MHz, CDCl3) δ 180.8, 170.4, 138.7, 136.8, 136.7, 128.2, 41.7; HRMS
(ESI): m/z [M + H]+ calcd for C8H10NO3S2: 232.0097; found: 232.0095.
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N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxo-2-(thiophen-3-yl)acetamide
(4u): Prepare according to the description in the general experimental
procedure. Yield 76%; 175.6 mg; yellow solid; mp 168−170 °C; IR (KBr): 1660,
1604, 1333, 1236, 1213, 1174, 806, 740 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.52
(s, 1H), 7.68 (d, J = 4.8 Hz, 1H), 7.33 (s, 1H), 3.44 (s, 6H); 13C{1H} NMR (75 MHz,
CDCl3) δ 182.7, 171.76, 137.7, 137.1, 127.9, 126.2, 41.96; HRMS (ESI): m/z [M +
H]+ calcd for C8H10NO3S2: 232.0097; found: 232.0090.
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2-(5-bromothiophen-2-yl)-N-(dimethyl(oxo)-6-sulfaneylidene)-2-oxoace
tamide (4v): Prepare according to the description in the general experimental
procedure. Yield 51%; 158.1 mg; yellow solid; mp 122−124 °C; IR (KBr): 1666,
1642, 1401, 1348, 1283, 1213, 1033, 875, 813 cm1; 1H NMR (600 MHz, CDCl3): δ
7.80 (d, J = 4.2 Hz, 1H), 7.07 (d, J = 4.2 Hz, 1H), 3.38 (s, 6H); 13C{1H} NMR (150
MHz, CDCl3) δ 178.7, 169.5, 139.2, 137.0, 131.2, 126.4, 41.79; HRMS (ESI): m/z
[M + H]+ calcd for C8H9BrNO3S2: 309.9202; found: 309.9209.
N-(dimethyl(oxo)-6-sulfaneylidene)-2-(2,5-dimethylthiophen-3-yl)-2-ox
oacetamide (4w): Prepare according to the description in the general
experimental procedure. Yield 42%; 108.8 mg; yellow solid; mp 104−106 °C; IR
1
(KBr): 1668, 1614, 1483, 1298, 1204, 1128, 1027 cm-1; H NMR (600 MHz,
13
CDCl3): δ 7.12 (s, 1H), 3.43 (s, 6H), 2.70 (s, 3H), 2.39 (s, 3H); C{1H} NMR (150
MHz, CDCl3) δ 184.9, 173.5, 151.6, 135.5, 131.3, 127.1, 42.1, 15.9, 14.9; HRMS
(ESI): m/z [M + H]+ calcd for C10H14NO3S2: 260.0409; found: 260.0410.
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N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxo-2-phenylacetamide (5a):
Prepare according to the description in the general experimental procedure.
Yield 48%; 120.5mg; yellow solid; mp 206−208 °C; IR (KBr): 1675, 1623, 1448,
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1410,1343, 1217, 1176, 718 cm-1; H NMR (600 MHz, CDCl3) δ 8.05 (d, J = 7.2
Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 3.75−3.68 (m, 2H),
3.46−3.38 (m, 2H), 2.40−2.37 (m, 2H), 2.34−2.31(, 2H); 13C{1H} NMR (150 MHz,
CDCl3) δ 190.3, 173.6, 134.2, 132.7, 130.0, 128.6, 53.1, 23.6; HRMS (ESI): m/z [M
+ H]+ calcd for C12H14NO3S: 252.0689; found: 252.0694.
N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxo-2-(p-tolyl)acetamide
(5b): Prepare according to the description in the general experimental
procedure. Yield 56%; 148.4 mg; yellow solid; mp 139−141 °C; IR (KBr): 1678,
1629, 1338, 1220, 1171, 1023, 900, 758 cm-1; 1H NMR (600 MHz, CDCl3) δ
7.95 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 3.73–3.69 (m, 2H), 3.42−3.97 (m,
2H), 2.42 (s, 3H), 2.39−2.36 (m, 2H), 2.33–2.30 (m, 2H); 13C{1H} NMR (150 MHz,
CDCl3) δ 190.0, 173.9, 145.3, 130.2, 130.1, 129.3, 53.1, 23.6, 21.8; HRMS (ESI):
m/z [M + Na]+ calcd for C13H15NNaO3S: 288.0665; found: 288.0664.
N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxo-2-(m-tolyl)acetamide
(5c): Prepare according to the description in the general experimental
procedure. Yield 45%; 119.3 mg; yellow solid; mp 141−143 °C; IR (KBr): 1680,
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1622, 1211, 1158, 1044, 809, 748 cm-1; 1H NMR (600 MHz, CDCl3) δ 7.85 (d, J =
7.2 Hz, 2H), 7.43 (d, J = 7.2 Hz, 1H), 7.37 (t, J = 7.8 Hz, 1H), 3.75–3.71 (m, 2H),
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3.45–3.41 (m, 2H), 2.41 (s, 3H), 2.40–2.35 (m, 2H), 2.34 –2.30(m, 2H); C{1H}
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NMR (150 MHz, CDCl3) δ 190.5, 173.8, 138.5, 135.1, 132.7, 130.3, 128.5, 127.5,
53.2, 23.6, 21.3; HRMS (ESI): m/z [M + Na]+ calcd for C13H15NNaO3S: 288.0665;
found: 288.0664.
2-(3-methoxyphenyl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoac
etamide (5d): Prepare according to the description in the general
experimental procedure. Yield 54%; 151.7 mg; yellow oil; IR (KBr): 1683, 1623,
1486, 1457, 1331, 1255, 1213, 1028 cm-1; 1H NMR (600 MHz, CDCl3) δ 7.63 (d, J
= 7.8 Hz, 1H), 7.57 (s, 1H), 7.39 (t, J = 7.8 Hz, 1H), 7.19–7.13 (m, 1H), 3.85 (s,
3H), 3.75–3.71 (m, 2H), 3.45–3.40 (m, 2H), 2.41–2.38 (m, 2H), 2.36–2.33 (m, 2H);
13C{1H} NMR (150 MHz, CDCl3) δ 190.2, 173.7, 159.7, 134.0, 129.7, 123.3, 121.2,
113.2, 55.4, 53.2, 23.6; HRMS (ESI): m/z [M + Na]+ calcd for C13H15NNaO4S:
304.0614; found: 304.0603.
2-(4-fluorophenyl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoaceta
mide (5e): Prepare according to the description in the general experimental
procedure. Yield 42%; 113 mg; yellow solid; mp 156–158 °C; IR (KBr): 1633,
1
1620, 1593, 1279, 1207, 1141, 1096, 906, 538 cm-1; H NMR (600 MHz, CDCl3)
δ 8.12–8.10 (m, 2H), 7.16 (t, J = 8.4 Hz, 2H), 3.76–3.71 (m, 2H), 3.46–3.41 (m,
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2H), 2.42–2.39 (m, 2H), 2.36–2.33 (m, 2H); C{1H} NMR (150 MHz, CDCl3) δ
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188.6, 173.3, 167.2, 133.0, 132.9, 129.3, 116.0, 115.8, 53.2, 23.6; HRMS (ESI):
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m/z [M + Na]+ calcd for C12H12FNNaO3S: 292.0414; found 292.0404.
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2-(4-chlorophenyl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoaceta
mide (5f): Prepare according to the description in the general experimental
procedure. Yield 52%; 148.2 mg; yellow solid; mp 125–127 °C; IR (KBr): 1682,
1
1619, 1402, 1340, 1212, 1169, 1082, 787 cm-1; H NMR (600 MHz, CDCl3) δ
8.02 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H), 3.75–3.70 (m, 2H), 3.46–3.41 (m,
13
2H), 2.46–2.38 (m, 2H), 2.38–2.30 (m, 2H); C{1H} NMR (150 MHz, CDCl3) δ
188.9, 173.0, 140.8, 131.5, 131.2, 129.0, 53.2, 23.7; HRMS (ESI): m/z [M + Na]+
calcd for C12H12ClNNaO3S: 308.0119; found 308.0107.
2-(3,4-dichlorophenyl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoa
cetamide (5g): Prepare according to the description in the general
experimental procedure. Yield 60%; 192 mg; yellow solid; mp 157–159 °C; IR
1
(KBr): 1665, 1624, 1384, 1316, 1202, 1175, 1077, 770 cm-1; H NMR (600 MHz,
CDCl3) δ 8.17 (s, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 3.79–3.69
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(m, 2H), 3.52–3.40 (m, 2H), 2.42–2.38(m, 2H), 2.35–2.31 (m, 2H); C{1H} NMR
(150 MHz, CDCl3) δ 187.6, 172.1, 138.8, 133.2, 132.5, 131.7, 130.7, 129.2, 53.2,
23.6; HRMS (ESI): m/z [M + Na]+ calcd for C12H11Cl2NNaO3S: 341.9734; found
341.9718.
2-(4-bromophenyl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoacet
amide (5h): Prepare according to the description in the general experimental
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procedure. Yield 49%; 161.7 mg; yellow solid; 137–139 °C; IR (KBr): 1684, 1617,
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1584, 1339, 1210, 1170, 1067, 1022, 816 cm-1; H NMR (400 MHz, CDCl3) δ
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7.94 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.4 Hz, 2H), 3.76–3.72 (m, 2H), 3.45–3.41 (m,
2H), 2.42–2.38 (m, 2H), 2.37–2.33 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3) δ
189.1, 172.9, 131.9, 131.6, 131.5, 129.6, 53.1, 23.6; HRMS (ESI): m/z [M + Na]+
calcd for C12H12BrNNaO3S: 351.9613; found 351.9600.
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methyl-4-(2-((1-oxidotetrahydrothiophen-1-ylidene)amino)-2-oxoacetyl)
benzoate (5i): Prepare according to the description in the general
experimental procedure. Yield 32%; 98.8 mg; yellow solid; mp 189–192 °C; IR
1
(KBr): 1719,1687, 1625, 1327, 1292, 1200, 1009, 725 cm-1; H NMR (600 MHz,
CDCl3) δ 8.13 (s, 4H), 3.95 (s, 3H), 3.77–3.72 (m, 2H), 3.48–3.43 (m, 2H),
2.42–2.39 (m, 2H), 2.36–2.34 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3) δ 189.4,
172.8, 166.0, 136.0, 134.6, 129.9, 129.6, 53.1, 52.5, 23.6; HRMS (ESI): m/z [M +
Na]+ calcd for C14H15NNaO5S: 332.0563; found 332.0551.
2-(naphthalen-2-yl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoacet
amide (5j): Prepare according to the description in the general experimental
procedure. Yield 62%; 108.6mg; yellow oil; IR (KBr): 1677, 1624, 1328, 1213,
1177, 1124, 750 cm-1; 1H NMR (600 MHz, CDCl3) δ 8.63 (s, 1H), 8.08 (d, J = 8.4
Hz, 1H), 7.97 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 8.4 Hz, 1H),
7.61 (t, J = 7.2 Hz, 1H), 7.55 (t, J = 7.2 Hz, 1H), 3.78–3.74 (m, 2H), 3.47–3.43 (m,
2H), 2.40–2.37(m, 2H), 2.35–2.32 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3) δ
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190.3, 173.8, 136.1, 133.3, 132.3, 130.1, 129.9, 129.1, 128.6, 127.8, 126.8, 124.3,
53.2, 23.6; HRMS (ESI): m/z [M + Na]+ calcd for C16H15NNaO3S: 324.0665;
found 324.0653.
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2-(naphthalen-1-yl)-N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxoacet
amide (5k): Prepare according to the description in the general experimental
procedure. Yield 65%; 195.7 mg; yellow solid; 212–214 °C; IR (KBr): 1665, 1624,
1384, 1316, 1202, 1175, 1077, 770 cm-1; 1H NMR (600 MHz, CDCl3) δ 9.02 (d, J
= 8.4 Hz, 1H), 8.12 (d, J = 6.6 Hz, 1H), 8.03 (d, J = 7.8 Hz, 1H), 7.86 (d, J = 7.8
Hz, 1H), 7.66–7.60 (m, 1H), 7.56–7.47 (m, 2H), 3.68–3.66 (m, 2H), 3.37–3.35 (m,
2H), 2.36–2.26 (m, 2H), 2.25–2.15 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3) δ
192.8, 174.0, 134.8, 133.63, 133.56, 130.8, 128.6, 128.53, 128.46, 126.5, 125.5,
124.3, 52.9, 23.4; HRMS (ESI): m/z [M + Na]+ calcd for C16H15NNaO3S:
324.0665; found 324.0654.
N-(1-oxidotetrahydrothiophen-1-ylidene)-2-oxo-2-(thiophen-3-yl)aceta
mide (5l): Prepare according to the description in the general experimental
procedure. Yield 50%; 128.5 mg; yellow solid; 179–181 °C; IR (KBr): 1651, 1621,
1226, 1158, 1018, 903, 542cm-1; 1H NMR (600 MHz, CDCl3) δ 8.54 (s, 1H), 7.67
(d, J = 4.8 Hz, 1H), 7.39–7.32 (m, 1H), 3.74–3.69 (m, 2H), 3.45–3.40(m, 2H),
2.39–2.36 (m, 2H), 2.31–2.28 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3) δ 182.7,
172.2, 137.7, 137.2, 127.8, 126.2, 53.0, 23.5; HRMS (ESI): m/z [M + Na]+ calcd
for C10H11NNaO3S2: 280.0073; found 280.0062.
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ASSOCIATED CONTENT
Supporting Information
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Crystallographic data and copies of the H and C NMR spectra are involved. This
material is available free of charge via the Internet at http://pubs.acs.joc.
AUTHOR INFORMATION
Corresponding Author
*E-mail: chwuax@mail.ccnu.edu.cn.
Author Contributions
+ P. Z and X. W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the National Natural Science Foundation of China
(Grant 21472056, 21602070, and 21772051) and the Fundamental Research
Funds for the Central Universities (CCNU15ZX002 and CCNU18QN011) for
financial support. It was also supported by the 111 Project B17019.
REFERENCES
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the preparation of solvent resistant polyimide nanofiltration membranes.
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Green Chem. 2011, 13, 162−168. (b) Martin, D.; Weise, A.; Niclas, H. J. The
Solvent Dimethyl Sulfoxide. Angew. Chem. Int. Ed. Engl. 1967, 6, 318−334.
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Synthon in Organic Chemistry. Synthesis 2016, 48, 1421−1436. and references
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(3) For selected examples, see: (a) Fei, H.; Yu, J.; Jiang, Y.; Guo, H.; Cheng, J. The
ammonium-promoted formylation of indoles by DMSO and H2O. Org. Biomol.
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Dimethyl Sulfoxide Participating in Copper(I) Iodide-Catalyzed Cascade
Oxidation/Formylation Reactions: The Synthesis of α-Formylpyrroles from
2,3-Dihydro-1H-pyrroles. Adv. Synth. Catal. 2014, 356, 3119−3124. (c) Ren, X.;
Chen, J.; Chen, F.; Cheng, J. The palladium-catalyzed cyanation of indole C–H
bonds with the combination of NH4HCO3 and DMSO as a safe cyanide source.
Chem. Commun. 2011, 47, 6725-6727. (d) Lv, Y.; Li, Y.; Xiong, T.; Pu, W.; Zhang,
H.; Sun, K.; Liu, Q.; Zhang, Q. Copper-catalyzed annulation of amidines for
quinazoline synthesis. Chem. Commun. 2013, 49, 6439−6441. (e) Xu, C.; Jiang,
S. F.; Wen, X. H.; Zhang, Q.; Zhou, Z. W.; Wu, Y. D.; Jia, F. C.; Wu, A. X. Dimethyl
Sulfoxide Serves as a Dual Synthon: Construction of 5-Methyl Pyrimidine
Derivatives via Four Component Oxidative Annulation. Adv. Synth. Catal. 2018,
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