PhI(OAc)2 co-promoted Amination Reaction: Synthesis of Î±

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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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The Journal of Organic Chemistry

I2/PhI(OAc)2 co-promoted Amination Reaction: Synthesis of α-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*† †Key

Laboratory of Pesticide & Chemical Biology, Ministry of Education,

College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China *E-mail: [email protected].

TOC Graphic: O Ar

+

H3C

O S

CH3

+

NH4HCO3

I2, PhI(OAc)2 130 oC

O Ar

N OH3C

S

CH3 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. 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. Scheme 1. Application of DMSO as “S/C2/O” source.


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Wang's work: Ar

a

N

N

Ar +

H3C

O S

Ar O CH3 N S N H3C O Ar

hv (365-370 nm) FeSO4 7H2O

CH3

H2O2

Cai's work: R3 HO Ar1

b

+

Ar2

H3C

O S

4CzIPN, PIFA 1,3,5-trimethoxybenzene blue LEDs

CH3

H3C

O S

O C Ar1 H2 R3 Ar2

This work: O

c

+

Ar

H3C

O S

CH3

+

I2/Ph(OAc)2

NH4HCO3

O N

Ar

S

OH3C

CH3 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 bicarbonate

we 2a

initial and

explore DMSO

the

acetophenone

reacting

at

80

°C

1a,

ammonium

afforded

the

α-dicarbonylsulfoximine 4a albeit in trace yield (Table 1, entry 1).



Page 4 of 36

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, Table 1. Optimization of the Reaction Conditionsa O

O +

NH4HCO3 +

1a

entry

2a

O S

N

I2, PhI(OAc)2 temp

O

3a

S

O

4a

Temp

PhI(OAc)2

I2

yield[b]

(°C)

(mmol)

(equiv)

(%)

1

80

2.5

1.6

trace

2

100

2.5

1.6

63

3

120

2.5

1.6

68

4

130

2.5

1.6

71

5

130

0.5

1.6

trace

6

130

1.0

1.6

5

7

130

2.0

1.6

40

8

130

2.75

1.6

70


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9

130

3.0

1.6

68

10

130

2.5

−

0

11

130

2.5

0.1

8

12

130

2.5

0.3

58

13

130

2.5

0.5

71

14

130

2.5

1.0

70

15

130

2.5

2.0

68

16c

130

2.5

0.5

0

17d

130

2.5

0.5

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. cIBX was used instead of PIDA. dPIFA was used

instead of PIDA.

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



Page 6 of 36

this reaction. However, no product was obtained in these cases (Table 1, entries 16−17). 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

+ NH4HCO3 +

R 1

2a

3a

S

O 4a 71% O N

S

O 4d 68%

4b 73% OMe O N

S

O

O

S

O

N

S

O 4m 54%

O

O Br 4k 50% O N

O

O S O

O 4p 40% O N

S

S

O 4s 60%

O 4q 77% O N

O

S

O

O

N O

S

S

S

O

Cl 4i 60% O N

O

O I 4l 65% O N

O MeOOC

S

S

O 4o 48%

O

O

O

S

S

O 4t 58%

N O

O

O 4r 78% O N S

O 4u 76%

S

S

O

O

O N

aReaction

O

O N

O

S

O 4f 54%

O N

Br

S

O 4n 62%

O

S

O O

Cl

4h 74% O N

4j 69% O

O

4c 78% O N

O

O Cl

S

O

O N

Cl

4g 72% O N

Ph

N O

O N

F

S

O 4e 45%

O

Br

S

O

O

O

O N

O

S

O 4

O N

Cl

R

130 oC

O

MeO

N

I2, PhI(OAc)2

O 4v 51%

S

N O

S

O

S

O

4w 42%

conditions: 1 (0.5 mmol), 2a (1.5 mmol), I2 (0.25 mmol) and PhI(OAc)2 (2.5 mmol)

heated in 4 mL of DMSO at 130 °C in a pressure vessel for 1 h. bProducts 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



Page 8 of 36

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. Scheme 3. Scope of the amination Reaction in Tetramethylene sulfoxide ab

+ NH4HCO3 +

R 1

I2, PhI(OAc)2

S O

2a

130 oC

5b 56% O S N

O

O

F

O S

O

O O

5j 62%

aReaction

N O

Cl

5f 52% O S

O

N O

N O

MeOOC

5h 49%

O S N

O S

O

O S

O

Br

5g 60%

5c 45%

5e 42%

N Cl

N O

O S N

O

O S

O

O

5a 48%

O

O

O S N

O

5d 54%

OMe

R

5

O

O

N

3b

O S N

O

Cl

O S

O

O

5i 32%

O S N

O O

O S

O

N S

5k 65%

O 5l 50%

conditions: 1 (0.5 mmol), 2a (1.5 mmol), I2 (0.25 mmol) and PhI(OAc)2 (2.5 mmol)

heated in 2 mL of tetramethylene sulfoxide at 130 °C in a pressure vessel for 1 h. bProducts 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). Scheme 4. Control Experiments



O

O

O O

I2, PhI(OAc)2 DMSO, 130 oC > 99% conversion

1a

1ab

O I

Ph

+

1aa

NH4HCO3

+

2a

O S

OH

+ H2O - H2O O

N

S

O

130 oC

3a

a

OH 1ac

I2, PhI(OAc)2

O b

4a 43% O

O OH

Ph

+

NH4HCO3

+

OH 1ac

2a

O I

Ph

+

1aa O

O S

o

130 C

3a HN S O

OH OH

+

1ac NH2

Ph O

+

S

O

Oc

4a 0% O N

I2, PhI(OAc)2 o

130 C

S

O

O d

4a 50% O

HN S O

130 oC

O S

N

I2, PhI(OAc)2

7a

O

N

I2, PhI(OAc)2

7a

Ph

6a

Page 10 of 36

S

O

O e

4a 49% O N

I2, PhI(OAc)2 o

130 C 3a

O

S

O f

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. Scheme 5. Proposed Mechanism PhI(OAc)2 2 AcOH

PhI(OAc)2 NH4HCO3

NH3

2a

2aa

Ph

I

NH

Ph A

2 AcOH

O S NH 7a

Ph

I

Ph 1a

HI

+

O S

O

1aa

O O

Ph HI + DMS

I

H

NH

Ph

I

Ph

N

1ab

I

B

O S

PhI

I2

path b +

H2O + PhI

path a

O

H2O

PhI O

N

O S

2 AcOH

O S N I Ph

PhI(OAc)2

C O

I2

O N

Ph 4aa OH

S

N

Ph O

2 HI

O 4a

S

O

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.



Experimental Section General Methods. 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 infrared spectrometer as KBr pellets with absorption in cm–1. 1H 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). 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. 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



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. 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, 1348, 1225, 1046 cm-1, 1H NMR (600 MHz, CDCl3): δ 8.04 (d, J = 7.8 Hz, 2H),


Page 14 of 36

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7.62 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 3.46 (s, 6H);

13C{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. 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, 1426, 1201, 1045, 810 cm-1; 1H NMR (600 MHz, CDCl3): δ 7.93 (d, J = 8.0 Hz, 2H), 7.28 (d, J =9.0 Hz, 2H), 3.45 (s, 6H), 2.42 (s, 3H);

13C{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,



Page 16 of 36

1619, 1259, 1510, 1426, 1254, 1224, 1196, 1168, 1081 cm-1; 1H NMR (300 MHz, CDCl3): δ 7.61 (d, J = 7.8 Hz, 1H), 7.58−7.53 (m, 1H), 7.44−7.35 (m, 1H), 7.20−7.13 (m, 1H), 3.86 (s, 3H), 3.45 (s, 6H);

13C{1H}

NMR (75 MHz, CDCl3) δ

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, 1633, 1287, 1215, 1149, 1033, 1008 cm-1; 1H 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, 6H);

13C{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 (KBr): 1668, 1611, 1375, 1266, 1227, 1096, 1028 cm-1; 1H 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 = 7.8 Hz, 2H), 7.46 (d, J = 7.8 Hz, 2H), 3.46 (s, 6H);

13C{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, 1612, 1581, 1347, 1219, 1201, 1045 cm-1; 1H 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, 1212 cm-1; 1H NMR (600 MHz, CDCl3): δ 7.71 (d, J = 8.4 Hz, 1H), 7.45 (s, 1H), 7.37 (d, J= 7.8 Hz, 1H), 3.43 (s, 6H);

13C{1H}

(150 MHz, CDCl3) δ 189.3, 170.8,



Page 18 of 36

139.3, 134.2, 132.60, 132.6, 130.2, 127.5, 41.5; HRMS (ESI): m/z [M + H]+ calcd for C10H10Cl2NO3S: 293.9753; found: 293.9751. 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, J = 8.4 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H), 3.46 (s, 6H);

13C{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, 1305, 1260, 1212, 1029 cm-1; 1H 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 = 7.2 Hz, 1H), 7.45 (s, 1H), 7.20 (s, 1H), 3.44 (s, 6H);


13C{1H}

NMR (150 MHz,

Page 19 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


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. 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. 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, 1287, 1215, 1149, 1033, 1008, 779 cm-1; 1H 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



(d, J = 10.2 Hz, 4H), 3.95 (s, 3H), 3.48 (s, 6H);

13C{1H}

Page 20 of 36


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. 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), 7.52−7.39 (m, 3H), 3.47 (s, 6H);

13C{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, 1606, 1331, 1309, 1255, 1232, 1170, 1043, 1020, 817 cm-1; 1H 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), 3.48 (s, 6H);

13C{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. 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, 1639, 1540, 1347, 1310, 1265, 1213, 1134, 1037 cm-1; 1H 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, 1603, 1408, 1237, 1217, 1057, 1034 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.14−8.01 (m, 1H), 7.80−7.73 (m, 1H), 7.20−7.12 (m, 1H), 3.47 (s, 6H);

13C{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.



Page 22 of 36

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. 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 (KBr): 1668, 1614, 1483, 1298, 1204, 1128, 1027 cm-1; 1H NMR (600 MHz, CDCl3): δ 7.12 (s, 1H), 3.43 (s, 6H), 2.70 (s, 3H), 2.39 (s, 3H);

13C{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, 1410,1343, 1217, 1176, 718 cm-1; 1H 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


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,



Page 24 of 36

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), 3.45–3.41 (m, 2H), 2.41 (s, 3H), 2.40–2.35 (m, 2H), 2.34 –2.30(m, 2H);

13C{1H}

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, 1620, 1593, 1279, 1207, 1141, 1096, 906, 538 cm-1; 1H 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, 2H), 2.42–2.39 (m, 2H), 2.36–2.33 (m, 2H);

13C{1H}



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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): m/z [M + Na]+ calcd for C12H12FNNaO3S: 292.0414; found 292.0404. 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, 1619, 1402, 1340, 1212, 1169, 1082, 787 cm-1; 1H 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, 2H), 2.46–2.38 (m, 2H), 2.38–2.30 (m, 2H);

13C{1H}


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 (KBr): 1665, 1624, 1384, 1316, 1202, 1175, 1077, 770 cm-1; 1H 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 (m, 2H), 3.52–3.40 (m, 2H), 2.42–2.38(m, 2H), 2.35–2.31 (m, 2H);

13C{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



procedure. Yield 49%; 161.7 mg; yellow solid; 137–139 °C; IR (KBr): 1684, 1617, 1584, 1339, 1210, 1170, 1067, 1022, 816 cm-1; 1H NMR (400 MHz, CDCl3) δ 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}


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. 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 (KBr): 1719,1687, 1625, 1327, 1292, 1200, 1009, 725 cm-1; 1H 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}



Page 26 of 36

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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. 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}


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.



ASSOCIATED CONTENT Supporting Information Crystallographic data and copies of the 1H and

13C

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: [email protected]. 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 (1) (a) Soroko, I.; Bhole, Y.; Livingston, A. G. Environmentally friendly route for the preparation of solvent resistant polyimide nanofiltration membranes.


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PhI(OAc)2 co-promoted Amination Reaction: Synthesis of Î±

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