Rh(III)-Catalyzed Direct Amination of Aromatic Ketoximes Enabled by Potassium Acetate

Article abstract of DOI:10.1002/ejoc.201901517

A method to achieve rhodium(III)-catalyzed, potassium acetate enabled intermolecular C–H amination of ketoximes using various benzenesulfonamide, especially 4-nitrobenzenesulfonamide is reported. Various aryl ketoximes substituted with electron-withdrawin

Full text of DOI:10.1002/ejoc.201901517

A Journal of
Accepted Article
Title: Rh(III)-catalyzed, potassium acetate enabled, ketoxime-assisted
direct amination of aromatic ketoximes
Authors: Lingling Liu, Ning Wang, Chenyang Dai, Yi Han, Shan Yang,
Zhibin Huang, and Yingsheng Zhao
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201901517
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
Rh(III)-catalyzed, potassium acetate enabled, ketoxime-assisted
direct amination of aromatic ketoximes
Lingling Liu,[a] Ning Wang,[a] Chenyang Dai,[a] Yi Han,[a] Shan Yang,[a] Zhibin Huang,*[a] Yingsheng
Zhao*[a]
Abstract: A method to achieve rhodium(III)-catalyzed, potassium acetate enabled intermolecular C-H amination of ketoximes using va
rious benzenesulfonamide, especially 4-nitrobenzenesulfonamide is reported. Various aryl ketoximes substituted with electron-withdrawi
ng functional groups were all well tolerated and produced the corresponding products in moderate to good yields. A preliminary mec
hanistic study revealed that potassium acetate is essential to realizing intermolecular amination.
Introduction
Transition metal-catalyzed C-N bond formation has been
extensively explored because these bonds are ubiquitous in
natural products and pharmaceuticals. Although the Buchwald-
Hartwig amination reaction and Ullmann-Goldberg coupling
reaction provide powerful methods for C-N bond formation, the
use of prefunctionalized arenes has limited the atomic economy
of these reactions1. Recently, direct catalytic C-H amination has
provided a high atomic economy and direct route to synthesize
(hetero) aryl amines2. This pioneering work was first reported
by Breslowet et al. who used an iron catalyst and imiono-iodane
Scheme 1. Metal catalyzed oxime-directed C-H amidation.
as the amidating reagent to realize the amidation of
cyclohexane3. Since then, various groups such as Chang4,
Ackermann5, Glorious6, Li7, Jiao8 and et al. have developed
efficient catalytic systems for C-H amination using Pd, Rh, Ir,
Results and Discussion
and Co using miscellaneous chloramines, organic azides, and
hydroxylamines as the aminating reagents. For example, Che
from ketoximes using 4-toluenesulfonamide and iodobenzene
et al. developed a palladium-catalyzed, oxime-directed C-H
Recently, we demonstrated the facile preparation of indazoles
diacetate in the presence of a rhodium(III) catalyst. A wide
amination method that uses an amide as the aminating
variety of nitro-substituted ketoximes were effectively used as
substrates, but the intermolecular amination product was easily
transformed into indazoles when using iodobenzene diacetate13.
We speculated that nitro-substituted ketoximes may be suitable
substrates for the intermolecular amination reaction if N-N
formation can be prevented during the rhodium(III) catalyzed
oxidative annulation of ketoximes with sulfonamides. With these
conditions in mind, we first explored the effects of oxidant to
identify whether the selective intermolecular amination could be
reagent9. Later, another group reported a Rh(III)-catalyzed
oxime-direct C(sp2)-H amination using N-chloramines (Scheme
1a)10. Recently, Zhao and co-workers disclosed the Rh(III)-
catalyzed C-H bond amination of O-methyl ketoximes with
sulfonamides (Scheme 1b)11. Although approaches to directly
introduce an amide group at the ortho position of O-methyl
ketoximes have been explored12, nitro-substituted O-methyl
ketoximes still remain a challenging class of substrates. Nitro
groups are indispensable in organic synthesis because they
can be easily converted to many other functional groups. Thus,
the development of a general procedure for C-H amination
compatible with nitro-containing substrates is highly important.
Herein, we report a Rh-catalyzed, potassium acetate enabled,
ketoxime-assisted direct amination of aromatic ketoximes
(Scheme 1c). The nitro-substituted aryl ketoximes were all
well tolerated and furnished the corresponding products in
moderate to good yields. A preliminary mechanistic study
revealed that potassium acetate was essential to realizing
intermolecular amination.
selectively
realized.
Thus,
we
firstly
treated
4-
nitroacetophenone oxime (1a) and 4-toluenesulfonamide (2a)
with various oxidants such as NaIO4, Na2S2O8, Cu(OAc)2, and
AgOAc. The results showed that NaIO4 provided the aminated
product 3a in 21% yield, along with 18% of the indazole product
4. The other oxidants all provided a mixture of 3a and 4 (Table
1, entry 1-4). Several bases, including K2CO3, KHCO3, and
KOAc, were employed when iodobenzene diacetate was used
as the oxidant(Table 1, entry 5-7). When KOAc was used as
the additive, only the intermolecular amination product 3a was
obtained in 87% yield. Unfortunately, when the reaction was
performed in the absence of AgSbF6, only a 23% yield of 3a
was obtained (Table 1, entry 8). A control experiment showed
that rhodium was necessary for this transformation.
[a] Key Laboratory of Organic Synthesis of Jiangsu Province, College of
Chemistry and Chemical Engineering, Soochow Unversity
199 Renai Street, Suzhou, Jiangsu 215123, China
E-mail: yszhao@suda.edu.cn
zbhuang@suda.edu.cn
1
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
Table 1. Optimization of Reaction Conditions. [a]
Encouraged by these results, we then explored the
functional group tolerance of ketoximes to 4-
nitrosulfonamide, and the results are presented in Table 3
.
3-nitroacetophenone oxime afforded 5b in 81% yield.
Other electron-withdrawing functional groups such as CF3,
SO2Me, CO2Me, and CN were all well tolerated (5c-5f),
giving the aminated products in good to excellent yields.
The bromide- or fluoride-substituted acetophenone oximes
only provided aminated products in moderate yields (5g-
5h), along with recovered starting material. Propiophenone
oxime (5i) and butyrophenone oxime (5j) both afforded
aminated products in good yields. 1-tetralone, 6-methoxy-
1-tetralone, xanthone, and chroman-4-one were all
Entry
Additive
Oxidant
Base
Yield % (3a /
4)
21/18
<5/23
10/14
8/26
26/7
31/12
87
1
2
3
4
5
6
7
8
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
AgSbF6
-
NaIO4
-
-
-
-
Na2S2O8
Cu(OAc)2
AgOAc
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
K2CO3
KHCO3
KOAc
KOAc
effective substrates
(5k-5n), generating the aminated
products in moderate to good yields. Interestingly, all
polysubstituted nitroacetophenone oximes performed well
when using 4-methylbenzenesulfonamide as the aminating
reagent (5o-5r), and gave the corresponding products in
moderate to good yields. In additionally, 4-(3,4-dichloro
phenyl)-tetralone (5s) was also a good substrate, affording
the aminated product in 58% yield. When the
acetophenone oxime derived from O-benzylhydroxylamine
was subjected to the standard reaction conditions, the
product 5t was obtained in 64% yield.
23
[a] Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), [Cp*RhCl2]2 (5 mol
%), AgSbF6 (20 mol %), Oxidant (2 equiv), Base (1 equiv), TFE (1.5 mL), 24
h; [b] isolated yields are given.
Once the optimized reaction conditions were determined, we
first explored the effect of different amides on this
transformation, and the data is listed in Table 2.
Benzenesulfonamide, 4-chlorobenzenesulfonamide, and
4-
methoxybenzenesulfonamideall provided the aminated products
in excellent yields (3b-3d). The nitro-substituted sulfonamides
all performed well, giving the corresponding products in greater
than 85% yields (3e-3g). It is worth mentioning that these nitro-
substituted sulfonamides could be easily removed under mild
conditions to afford the aromatic amine compounds.
Trifluoromethanesulfonamide was well tolerated, yielding the
aminated products in 93% yield (3h). Unfortunately,
trifluoroacetamide only provided the aminated product 3j in 35%
yield.
Table 3. Substrate Scope of Ketoximes. [a]
Table 2. The Amide Effect. [a]
[a] Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), [Cp*RhCl2]2 (5 mol
%), AgSbF6 (20 mol %), PhI(OAc)2 (2 equiv), KOAc (1 equiv), TFE (1.
5 mL), 24 h; [b] isolated yields are given. [c] Without AgSbF6 and KOAc.
To further demonstrate the synthetic utility of this method,
a gram-scale reaction was performed. The product 3g was
obtained in 78% yield when the reaction was performed at
a 10 mmol scale (Scheme 2a). The oxime directing group
[a] Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), [Cp*RhCl2]2 (5 mol %),
AgSbF6 (20 mol %), PhI(OAc)2 (2 equiv), KOAc (1 equiv),TFE (1.5 mL), 24 h;
[b] isolated yields are given.
2
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
(
Scheme 2d
)
and these nitro-substituted sulfonamides
Based on a previous report and these results15, a
plausible reaction pathway is proposed in Scheme 4. The
cationic [Cp*RhIII]2+ complex first coordinated with the
(
Scheme 2c) were easily removed, and the nitro functional
group (Scheme 2b) was easily reduced to an amine14.
ketoxime and produced complex
activation. The iodonium was formed in situ from the
sulfonamide using iodobenzene diacetate, which reacted
with complex to afford complex II, followed by migratory
I via oxime-assisted C-H
Scheme 2. Applications of the reaction.
x
I
insertion to provide complex III. Subsequent protonation
would release the aminated product 3a and the catalyst
precursor.
To figure out the role of potassium acetate during the
catalytic cycle, several parallel experiments were carried
out. When product 3a was treated with iodobenzene
diacetate, the indazole product 4 was obtained in 51% yield
(
Scheme 5a). The free radical scavenger TEMPO can
completely shut down this cyclization reaction (Scheme
5b), indicating it undergoes an iodobenzene diacetate
induced free radical pathway. Based on the previous work of
Lee13a and these results, a plausible mechanism to form
4
was proposed in Scheme 6. When product 3a is treated with
iodobenzene acetate, the key intermediate A would be formed.
The N-I bond splitting can provide the intermediate B, followed
by N-N bond formation and electronic transfer to afford the
product 4.
Scheme 5. Further Mechanistic Study.
A simple mechanism experiment was performed to gain
insight into this rhodium(III)-catalyzed C-H amination
reaction (Scheme 3). When iodonium x was used, the
corresponding product 3a was obtained in 52% yield. This
result may indicate the in situ generation of
x from the
amide with iodobenzene diacetate as the key intermediate
during the catalytic cycle.
Scheme 3. Preliminary Mechanistic Study.
Scheme 6. Plausible pathway from 3a to 4
Scheme 4. Proposed Mechanism.
Scheme 7. The role of potassium acetate.
However, the indazole product
4 was not formed when 1
equivalent of potassium acetate was used as the additive.
When the amount of potassium was reduced to less than
30 mol%, the yield of
4
is not greatly affected (Scheme 7).
3
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
O-methyl oxime . 1.72 g, 49 % yield. White Solid. mp: 99-100 oC.
1H NMR (400 MHz, CDCl3) δ 8.11–8.04 (m, 1H), 7.35 (d, J = 8.3
Hz, 1H), 7.29–7.21 (m, 2H), 7.18 (d, J = 2.1 Hz, 1H), 6.92–6.87
(m, 2H), 4.11–4.06 (m, 1H), 4.00 (s, 3H), 2.74–2.57 (m, 2H), 2.35–
2.13 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 153.1, 144.3, 139.7, 1
32.5, 130.9, 130.5 – 130.2 (m), 129.3, 128.9, 127.8, 127.2, 124.3,
62.0, 44.1, 29.3, 21.2. HRMS Calcd for C17H15Cl2NNaO [M+Na]+: 34
2.0428; Found: 342.0418.
It might be large amount of amount acetate anions would
decompose key intermediate
A to the starting material 3a
(Scheme 6).
Conclusions
Here, we have developed
a
practical Rh-catalyzed,
potassium acetate enabled, ketoxime-assisted direct amination
of aromatic ketoximes. Various aryl ketoximes substituted with
electron-withdrawing functional groups were all well tolerated
and gave the corresponding products in moderate to good
yields. Preliminary mechanistic studies revealed the potassium
acetate is essential to realize the intermolecular amination.
General procedure for the synthesis of products A mixture of O-
methyl ketoximes 1 (0.2 mmol, 1.0 equiv), Sulfonamide derivatives 2
(0.4 mmol, 2 equiv), [RhCp*Cl2]2 (6.2 mg, 0.05 equiv), AgSbF6 (14.0 mg,
0.2 equiv), PhI(OAc)2 (128.8 mg, 2 equiv), KOAc ( 19.6 mg, 1 equiv)
Trifluoroethanol (1.5 mL) in a 15 mL glass vial was heated at 90 oC for
24 hours. The reaction mixture was cooled to rt, filtered through
diatomite and washed with 5-10 mL of ethyl acetate then concentrated
in vacuo. The resulting residue was purified by column chromatography
with the solvent of PE/EA= 15:1 on silica gel to give the product.
Experimental Section
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)-4-methylbenzenesulfonamid
1
e (3a) 55.9 mg, 87 % yield. Pale yellow solid; mp: 167-168 oC;
General procedures. Unless otherwise noted, all reagents were p
urchased from commercial suppliers and used without further purific
ation. [RhCp*Cl2]2 was prepared according to the literature procedur
es16-17. Column chromatography purifications were performed using
300–400 mesh silica gel. NMR spectra were obtained on Bruker D
RX–400 instrument. Multiplicities are recorded as: s = singlet, d =
doublet, t = triplet, br = broad, m = multiplet. The 1H NMR (400 M
Hz) chemical shifts were measured relative to CDCl3, TMS or DMS
O-d6 as the internal reference (CDCl3: δ = 7.26 ppm; TMS: δ = 0.0
0 ppm; DMSO-d6: δ = 2.50 ppm). The 13C NMR (100 MHz) chemic
al shifts were given using CDCl3 or DMSO-d6 as the internal standa
rd (CDCl3: δ = 77.00ppm; DMSO-d6: δ = 39.52 ppm). HRMS analy
ses were carried out using a Bruker MicrOTOF-Q II instrument.
H NMR (400 MHz, CDCl3) δ 11.17 (br, 1H), 8.45 (d, J = 2.3 Hz, 1
H), 7.85 (d, J = 2.3 Hz, 1H), 7.73 (d, J = 8.3 Hz, 2H), 7.50 (d, J
= 8.8 Hz, 1H), 7.26 (d, J = 4.0 Hz, 2H), 4.14 (s, 3H), 2.38 (s, 3H),
2.17 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 154.7, 147.3, 143.8, 1
36.9, 135.6, 129.3, 128.8, 127.4, 126.9, 117.1, 114.1, 62.7, 21.1, 1
2.8. HRMS Calcd for C16H17N3NaO5S [M+Na]+: 386.0787; Found: 38
6.0784.
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)benzenesulfonamide (3b) 4
8.8 mg, 70 % yield; Pale yellow solid. mp: 180-181 oC; 1H NMR (4
00 MHz, CDCl3) δ 11.18 (br, 1H), 8.47 (d, J = 2.3 Hz, 1H), 7.88
(dd, J = 8.8, 2.4 Hz, 1H), 7.86–7.80 (m, 2H), 7.54 (dd, J = 5.0, 3.
7 Hz, 1H), 7.52–7.44 (m, 3H), 4.14 (s, 3H), 2.15 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 154.7, 147.3, 138.5, 136.7, 132.8, 128.7, 128.
7, 127.8, 126.8, 117.4, 114.5, 62.7, 12.8. HRMS Calcd for C15H15N3
NaO5S [M+Na]+: 372.0630; Found: 372.0615.
Preparation of O-methyl ketoximes (1a-1l, 1n-1r, 1t): Add ketones
(11.0 mmol),pyridine (2.5 mL, 30.9 mmol), H2OMe•HCl (1.14 g,
16.5mmol), EtOH (5 mL) to a 100 mL round bottom flask equipped with
a stir bar, stirred at 60 oC for 6 h. Subsequently, the mixture was
quenched with water and extracted twice with ethyl acetate.The organic
phases were combined, washed once with aqueous HCl and brine, dried
over Na2SO4. The solvents were removed under reduced pressure.
Recrystallization from ethyl acetate to give the O-methyl ketoximes.
4-Chloro-N-(2-(1-(methoxyimino)ethyl)-5-nitrophenyl)benzenesulfonamid
e (3c) 57.4 mg, 75 % yield. Pale yellow solid; mp: 164-166 oC; 1H
NMR (400 MHz, CDCl3) δ 11.27 (br, 1H), 8.45 (d, J = 2.3 Hz, 1
H), 7.90 (dd, J = 8.8, 2.3 Hz, 1H), 7.81–7.71 (m, 2H), 7.54 (d, J =
8.8 Hz, 1H), 7.48–7.39 (m, 2H), 4.14 (s, 3H), 2.20 (s, 3H). 13C N
MR (100 MHz, CDCl3) δ 154.8, 147.3, 139.5, 136.9, 136.5, 129.1,
129.0, 128.2, 127.5, 117.6, 114.2, 62.72, 12.8. HRMS Calcd for C15
H14ClN3NaO5S [M+Na]+: 406.0240; Found: 406.0236.
Spectral data matched those previously reported 11,18
.
Preparation of O-methyl 9H-xanthen-9-one O-methyl oxime (1m).
Add 9H-xanthen-9-one (11.0 mmol), pyridine (2.5 mL, 30.9 mmol),
H2OMe•HCl (1.14 g, 16.5mmol), EtOH (5 mL) to a 100 mL round bottom
flask equipped with a stir bar, stirred at 60 oC for 6 h. Subsequently, the
mixture was quenched with water and extracted twice with ethyl
acetate.The organic phases were combined, washed once with aqueous
HCl and brine, dried over Na2SO4. The solvents were removed under
reduced pressure. Recrystallization from ethyl acetate to give the 9H-
xanthen-9-one O-methyl oxime. 1.42 g, 57 % yield. White solid. mp: 71-
72 oC. 1H NMR (400 MHz, CDCl3) δ 8.85 (d, J = 8.2 Hz, 1H), 8.09 (d, J =
4-Methoxy-N-(2-(1-(methoxyimino)ethyl)-5-nitrophenyl)benzenesulfona
mide (3d) 67.4 mg, 89 % yield. Pale yellow solid; mp: 157-158 oC;
1H NMR (400 MHz, CDCl3) δ 11.16 (br, 1H), 8.44 (d, J = 2.3 Hz,
1H), 7.85 (dd, J = 8.8, 2.3 Hz, 1H), 7.81–7.74 (m, 2H), 7.51 (d, J
= 8.8 Hz, 1H), 6.94–6.87 (m, 2H), 4.14 (s, 3H), 3.82 (s, 3H), 2.19
(s, 3H). 13C NMR (100 MHz, CDCl3) δ 163.4, 155.2, 147.7, 137.5,
130.4, 129.5, 129.3, 127.8, 117.5, 114.4, 114.3, 63.2, 55.7, 13.3.
HRMS Calcd for C16H17N3NaO6S [M+Na]+: 402.0732; Found: 402.07
24.
7.9 Hz, 1H), 7.50–7.36 (m, 2H), 7.28–7.12 (m, 4H), 4.12 (s, 3H).13
C
NMR (100 MHz, CDCl3) δ 152.7, 151.3, 139.9, 131.6, 131.4, 130.3,
124.3, 123.5, 122.5, 119.3, 117.2, 116.7, 116.5, 62.9. HRMS Calcd for
C14H11NNaO2 [M+Na]+: 248.0687;Found: 248.0683.
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)-3-nitrobenzenesulfonamide
(3e) 70.9 mg, 90 % yield. Yellow solid; mp: 123-125 oC; 1H NMR
(400 MHz, CDCl3) δ 11.43 (s, 1H), 8.66 – 8.60 (m, 1H), 8.45 (d, J
= 2.3 Hz, 1H), 8.41 – 8.37 (m, 1H), 8.19–8.14 (m, 1H), 7.94–7.89
(m, 1H), 7.74–7.68 (m, 1H), 7.57 (d, J = 8.8 Hz, 1H), 4.17 (s, 3
H), 2.19 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.3, 148.3, 147.8,
141.1, 136.4, 132.7, 130.6, 129.7, 128.2, 127.7, 122.3, 118.6, 114.
9, 63.3, 13.2. HRMS Calcd for C15H14N4NaO7S [M+Na]+: 417.0481;
Found: 417.0498.
Preparation of 4-(3,4-dichlorophenyl)-3,4-dihydronaphthalen-1(2H)
-one O-methyl oxime (1s). Add 4-(3,4-dichlorophenyl)-3,4-dihydrona
phthalen-1(2H)-one (11.0 mmol), pyridine (2.5 mL, 30.9 mmol), H2O
Me•HCl (1.14 g, 16.5mmol), EtOH (5 mL) to a 100 mL round botto
m flask equipped with a stir bar, stirred at 60 oC for 6 h. Subsequ
ently, the mixture was quenched with water and extracted twice wit
h ethyl acetate.The organic phases were combined, washed once w
ith aqueous HCl and brine, dried over Na2SO4. The solvents were r
emoved under reduced pressure. Recrystallization from ethyl acetate
to give the 4-(3,4-dichlorophenyl)-3,4-dihydronaphthalen-1(2H)-one
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)-2-nitrobenzenesulfonamide
(3f) 66.9 mg, 85 % yield. Pale yellow solid; mp:185-186 oC; 1H N
4
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
MR (400 MHz, CDCl3) δ 11.82 (br, 1H), 8.58 (d, J = 2.3 Hz, 1H),
8.30–8.26 (m, 1H), 7.91 (dd, J = 8.8, 2.3 Hz, 1H), 7.88–7.84 (m, 1
H), 7.79–7.74 (m, 2H), 7.58 (d, J = 8.8 Hz, 1H), 4.23 (s, 3H), 2.25
(s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.8, 147.5, 147.2 135.9,
133.9, 132.3, 132.1, 131.2, 129.1, 127.9, 125.1, 117.3, 112.9, 62.8,
12.9. HRMS Calcd for C15H15N4O7S [M+H]+: 395.0661; Found: 395.
0659.
13.2. HRMS Calcd for C16H17N3NaO7S2 [M+Na]+: 450.0406; Found:
450.0390.
4-(1-(Methoxyimino)ethyl)-3-(4-nitrophenylsulfonamido)benzoate (5e) 5
2.9 mg, 75 % yield. Pale yellow solid; mp: 153-155 oC; 1H NMR (4
00 MHz, CDCl3) δ 11.15 (br, 1H), 8.28–8.25 (m, 2H), 8.24 (d, J =
1.9 Hz, 1H), 7.99–7.88 (m, 2H), 7.77 (dd, J = 8.3, 1.9 Hz, 1H), 7.
13
43 (d, J = 8.3 Hz, 1H), 4.11 (s, 3H), 3.93 (s, 3H), 2.10 (s, 3H).
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)-4-nitrobenzenesulfonamid
e(3g) 68.6 mg, 87 % yield. Yellow solid; mp: 173-175 oC; 1H NM
R (400 MHz, CDCl3) δ 11.52 (br, 1H), 8.47 (d, J = 2.3 Hz, 1H), 8.
35–8.28 (m, 2H), 8.07–8.00 (m, 2H), 7.93 (dd, J = 8.8, 2.3 Hz, 1
H), 7.57 (d, J = 8.8 Hz, 1H), 4.16 (s, 3H), 2.22 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 155.4, 150.4, 147.9, 144.7, 136.5, 129.7, 128.
8, 127.8, 124.5, 118.4, 114.5, 63.3, 13.3. HRMS Calcd for C15H14N4
NaO7S [M+Na]+: 417.0481; Found: 417.0498.
C NMR (100 MHz, CDCl3) δ 165.2, 155.3, 149.7, 144.5, 134.8, 130.
9, 128.4, 128.0, 126.9, 124.9, 123.7, 121.4, 62.5, 52.1, 12.7. HRM
S Calcd for C17H17N3NaO7S [M+Na]+: 430.0685; Found: 430.0702.
N-(4-Cyano-2-(1-(methoxyimino)ethyl)phenyl)-4-nitrobenzenesulfonamid
e (5f) 59.0 mg, 79 % yield. Pale yellow solid; mp: 155-156 oC; 1H
NMR (400 MHz, CDCl3) δ 11.88 (br, 1H), 8.32 (d, J = 9.0 Hz, 2H),
8.02 (d, J = 9.0 Hz, 2H), 7.71 (d, J = 2.3 Hz, 1H), 7.70 (d, J =
4.3 Hz, 1H), 7.54 (dd, J = 4.3, 2.3 Hz, 1H), 4.13 (s, 3H), 2.23 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 154.9, 149.9, 144.4, 139.1, 132.
8, 132.4, 127.9, 124.1, 122.3, 118.7, 117.4, 107.0, 62.7, 12.4. HRM
S Calcd for C15H14N4NaO5S [M+Na]+: 374.0685; Found: 374.0680.
1,1,1-Trifluoro-N-(2-(1-(methoxyimino)ethyl)-5-nitrophenyl)methanesulfo
namide (3h) 63.4 mg, 94 % yield. Pale yellow solid; mp: 66-68 oC;
1H NMR (400 MHz, CDCl3) δ 12.18 (br, 1H), 8.62 (d, J = 2.3 Hz,
1H), 8.13 (dd, J = 8.8, 2.3 Hz, 1H), 7.77 (d, J = 8.8 Hz, 1H), 4.1
13
6 (s, 3H), 2.44 (s, 3H). 19F NMR (400 MHz, CDCl3) δ -76.43 (s).
N-(5-Bromo-2-((methoxyimino)(phenyl)methyl)phenyl)-4-nitrobenzenesul
fonamide (5g) 39.1 mg, 40 % yield. Pale yellow solid; mp: 170-171
oC; 1H NMR (400 MHz, CDCl3) δ 11.09 (br, 1H), 8.33–8.25 (m, 2
H), 8.01–7.97 (m, 2H), 7.89 (d, J = 2.0 Hz, 1H), 7.3-7.4 (m, 3H),
7.09 (dd, J = 8.5, 2.0 Hz, 1H), 6.93–6.85 (m, 2H), 6.63 (d, J = 8.5
Hz, 1H), 4.06 (s, 3H).13C NMR (100 MHz, CDCl3) δ 157.6, 150.3,
144.9, 136.7, 133.1, 131.4, 130.3, 129.7, 128.4, 127.7, 127.6, 124.
3, 124.5, 124.2, 122.9, 63.3. HRMS Calcd for C20H16BrN3NaO5S [M
+Na]+: 511.9892; Found: 511.9902.
C NMR (100 MHz, CDCl3) δ 154.9, 147.5, 135.1, 129.1, 127.8, 119.
1, 114.9, 62.8, 12.8. HRMS Calcd for C10H10F3N3NaO5S [M+Na]+: 3
64.0191; Found: 364.0197.
N-(2-(1-(Methoxyimino)ethyl)-5-nitrophenyl)methanesulfonamide (3i) 5
1.6 mg, 90 % yield. Pale yellow solid; mp: 175-177 oC; 1H NMR (4
00 MHz, CDCl3) δ 11.14 (br, 1H), 8.49 (d, J = 2.3 Hz, 1H), 7.95
(dd, J = 8.8, 2.3 Hz, 1H), 7.67 (d, J = 8.8 Hz, 1H), 4.10 (s, 3H),
3.12 (s, 3H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.0, 14
7.6, 137.3, 129.3, 126.5, 116.9, 112.7, 62.7, 40.2, 12.9. HRMS Cal
cd for C10H13N3NaO5S [M+Na]+: 310.0474; Found: 310.0458.
N-(5-Fluoro-2-(1-(methoxyimino)ethyl)phenyl)-4-nitrobenzenesulfonamid
e (5h) 33.0 mg, 45 % yield. Yellow solid; mp: 136-137 oC; 1H NM
R (400 MHz, CDCl3) δ 11.54 (br, 1H), 8.27 (d, J = 8.8 Hz, 2H), 7.
96 (d, J = 8.8 Hz, 2H), 7.43–7.32 (m, 2H), 6.83-6.79 (m, 1H), 4.08
(s, 3H), 2.11 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 164.0, 161.5,
155.8, 150.2, 144.9, 137.2 (d, J-F = 10.9 Hz), 130.5 (d, J-F = 10.
0 Hz), 128.4, 124.2, 119.4, 111.4 (d, J-F = 21.8 Hz), 107.8 (d, J-F
= 26.6 Hz), 62.7, 13.1. 19F NMR (400 MHz, CDCl3) δ -107.81 (s).
HRMS Calcd for C15H14FN3NaO5S [M+Na]+: 390.0536; Found: 390.
0544.
2,2,2-Trifluoro-N-(2-(1-(methoxyimino)ethyl)-5-nitrophenyl)acetamide (3j)
21.3 mg, 35 % yield. Pale yellow solid; mp: 135-136 oC; 1H NMR
(400 MHz, CDCl3) δ 12.64 (br, 1H), 9.46 (d, J = 2.4 Hz, 1H), 8.0
6 (dd, J = 8.8, 2.4 Hz, 1H), 7.72 (d, J = 8.8 Hz, 1H), 4.09 (s, 3H),
2.39 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.2, 154.9 (d, J-F =
38.0 Hz), 147.4, 135.4, 128.8, 127.4, 118.9, 115.5, 113.8, 62.4, 12.
9. 19F NMR (400 MHz, CDCl3) δ -75.91. HRMS Calcd for C11H10F3
N3NaO4 [M+Na]+: 328.0521; Found: 364.0516.
N-(2-(1-(Methoxyimino)propyl)phenyl)-4-nitrobenzenesulfonamide (5i)
Yellow liquid. 42.8 mg, 59 % yield; 1H NMR (400 MHz, CDCl3) δ 1
1.23 (br, 1H), 8.23 (d, J = 8.8 Hz, 2H), 7.89 (d, J = 8.8 Hz, 2H),
7.68 (d, J = 7.4 Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 7.34–7.27 (m,
1H), 7.19–7.09 (m, 1H), 4.07 (s, 3H), 2.58 (q, J = 7.6 Hz, 2H), 0.9
3 (t, J = 7.6 Hz, 3H). 13C NMR (100MHz, CDCl3) δ 161.2, 150.0,
145.2, 135.5, 130.0, 128.4, 128.4, 124.9, 124.0, 122.8, 121.7, 62.7,
20.1, 11.0. HRMS Calcd for C16H18N3O5S [M+H]+: 364.0967; Found:
364.0958.
N-(2-(1-(Methoxyimino)ethyl)-4-nitrophenyl)-4-nitrobenzenesulfonamide
(5b) 63.8 mg, 81 % yield. Pale yellow solid; mp: 175-176 oC; 1H
NMR (400 MHz, CDCl3) δ 12.09 (br, 1H), 8.36–8.30 (m, 3H), 8.13
(dd, J = 9.1, 2.6 Hz, 1H), 8.07–8.03 (m, 2H), 7.74 (d, J = 9.1 Hz,
1H), 4.15 (s, 3H), 2.32 (s, 3H).13C NMR (100 MHz, CDCl3) δ 155.
3, 150.0, 144.3, 142.7, 140.8, 128.0, 124.6, 124.1, 121.7, 117.9, 62.
7, 12.5. HRMS Calcd for C15H14N4NaO7S [M+Na]+: 417.0481; Found:
417.0491.
N-(2-(1-(Methoxyimino)ethyl)-5-(trifluoromethyl)phenyl)-4-nitrobenzenes
N-(2-(1-(Methoxyimino)butyl)phenyl)-4-nitrobenzenesulfonamide (5j) Y
ellow liquid. 45.8 mg, 61 % yield. 1H NMR (400 MHz, CDCl3) δ 11.
31 (br, 1H), 8.24–8.20 (m, 2H), 7.92–7.87 (m, 2H), 7.70 (m, 1H), 7.
37 (dd, J = 8.0, 1.4 Hz, 1H), 7.33–7.27 (m, 1H), 7.13 (dd, J = 8.0,
1.4Hz, 1H), 4.06 (s, 3H), 2.64–2.47 (m, 2H), 1.39–1.21 (m, 2H), 0.
85 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 160.2, 150.0,
145.3, 135.5, 129.9, 128.6, 128.3, 124.7, 124.0, 122.7, 121.5, 62.7,
28.4, 20.1, 14.1. HRMS Calcd for C17H20N3O5S [M+H]+: 378.1124;
Found: 378.1132.
ulfonamide (5c) 60.0 mg, 72 % yield. Pale yellow solid; mp: 120-12
2
oC; 1H NMR (400 MHz, CDCl3) δ 11.31 (br, 1H), 8.30–8.24 (m,
2H), 7.96–7.94 (m, 1H), 7.93 (s, 2H), 7.49 (d, J = 8.3 Hz, 1H), 7.3
6 (d, J = 8.3, 1H), 4.12 (s, 3H), 2.13 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 155.6, 150.3, 144.8, 135.8, 131.8 (q, J-F = 33.2 Hz), 12
9.3, 128.4, 126.4, 124.3, 121.0 (d, J-F = 3.8 Hz), 117.6 (d, J-F =
3.9 Hz), 63.1, 13.1. 19F NMR (400 MHz, CDCl3) δ -63.20(s). HRMS
Calcd for C16H14F3N3NaO5S [M+Na]+: 440.0504; Found: 440.0511.
N-(2-(1-(Methoxyimino)ethyl)-5-(methylsulfonyl)phenyl)-4-nitrobenzenes
N-(8-(Methoxyimino)-5,6,7,8-tetrahydronaphthalen-1-yl)-4-nitrobenzenes
ulfonamide (5k) 43.4 mg, 58 % yield. White solid; mp: 204-205 oC;
1H NMR (400 MHz, CDCl3) δ 11.72 (br, 1H), 8.27–8.19 (m, 2H), 7.
97–7.90 (m, 2H), 7.47 (d, J = 7.2 Hz, 1H), 7.19-7.15 (m, 1H), 6.88
(dd, J = 7.6, 1.0 Hz, 1H), 4.07 (s, 3H), 2.70–2.59 (m, 4H), 1.70–1.
61 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 157.4, 149.9, 145.3, 14
2.1, 136.0, 129.9, 129.4, 128.4, 124.9, 124.7, 123.9, 118.4, 118.3,
ulfonamide (5d) 76.0 mg, 89 % yield. Pale yellow solid; mp: 146-14
8
oC; 1H NMR (400 MHz, CDCl3) δ 11.48 (br, 1H), 8.33–8.27 (m,
2H), 8.17 (d, J = 1.8 Hz, 1H), 8.05–7.98 (m, 2H), 7.65 (dd, J = 8.
4, 1.8 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 4.14 (s, 3H), 3.06 (s, 3
H), 2.20 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.5, 150.4, 144.6,
141.5, 136.4, 129.8, 128.9, 127.1, 124.4, 122.3, 118.3, 63.2, 44.2,
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201901517
European Journal of Organic Chemistry
62.7, 30.6, 24.9, 20.6. HRMS Calcd for C17H17N3NaO5S [M+Na]+: 39
8.0787; Found: 398.0777.
N-(4-(3,4-Dichlorocyclohexa-1,5-dien-1-yl)-8-(methoxyimino)-5,6,7,8-tetr
ahydronaphthalen-1-yl)-4-nitrobenzenesulfonamide (5s) 60.4 mg, 58
% yield. Pale yellow solid; mp: 179-180 oC; 1H NMR (400 MHz, C
DCl3) δ 11.81 (br, 1H), 8.29 (d, J = 8.8 Hz, 2H), 7.98 (d, J = 8.8
Hz, 2H), 7.55 (d, J = 7.6 Hz, 1H), 7.32 (d, J = 8.3 Hz, 1H), 7.19-
7.17 (m, 1H), 6.98 (d, J = 2.0 Hz, 1H), 6.74 (dd, J = 8.3, 2.0 Hz,
1H), 6.68 (d, J = 7.6 Hz, 1H), 4.09 (s, 3H), 4.04 (t, J = 5.3 Hz, 1
H), 2.74-2.66 (m, 1H), 2.54-2.45 (m, 1H), 2.01-1.95 (m, 2H). 13C N
MR (100 MHz, CDCl3) δ 156.7, 150.1, 145.3, 143.7, 142.1, 136.3,
132.7, 130.8, 130.5, 130.1, 130.0, 128.5, 127.5, 125.6, 124.1, 119.2,
118.4, 62.9, 44.4, 27.9, 21.6. HRMS Calcd for C23H21Cl2N3NaO5S
[M+Na]+: 502.0371; Found: 502.0364.
N-(3-Methoxy-8-(methoxyimino)-5,6,7,8-tetrahydronaphthalen-1-yl)-4-nit
robenzenesulfonamide (5l) 43.6 mg, 54 % yield. Pale yellow solid;
mp: 145-147 oC; 1H NMR (400 MHz, CDCl3) δ 11.97 (br, 1H), 8.3
1–8.20 (m, 2H), 8.02–7.90 (m, 2H), 7.05 (d, J = 2.6 Hz, 1H), 6.40
(d, J = 2.6 Hz, 1H), 4.04 (s, 3H), 3.78 (s, 3H), 2.65-2.61 (m, 4H),
1.69-1.59 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 160.1, 157.4, 15
0.0, 145.3, 143.6, 137.9, 128.5, 124.0, 111.2, 110.1, 103.9, 62.5, 5
5.3, 31.0, 24.9, 20.6. HRMS Calcd for C18H19N3NaO6S [M+Na]+: 428.
0992; Found: 428.0982.
N-(2-(1-((Benzyloxy)imino)ethyl)-5-nitrophenyl)-4-nitrobenzenesulfonami
de (5t) 60.0 mg, 64 % yield. Pale yellow solid; mp: 168-169 oC; 1H
NMR (400 MHz, CDCl3) δ 11.34 (br, 1H), 8.48 (d, J = 2.1 Hz, 1
H), 8.13 (d, J = 8.7 Hz, 2H), 7.89 (dd, J = 8.8, 2.1 Hz, 1H), 7.61
(d, J = 8.7 Hz, 2H), 7.56 (d, J = 8.8 Hz, 1H), 7.54–7.41 (m, 5H),
5.35 (s, 2H), 2.28 (s, 3H).13C NMR (100 MHz, CDCl3) δ 156.2, 150.
2, 147.8, 144.5, 136.9, 136.6, 129.7, 129.0, 128.7, 128.6, 128.5 , 1
27.5, 124.3, 118.2, 114.1, 13.5. HRMS Calcd for C21H18N4NaO7S [M
+Na]+: 470.0896; Found: 470.0891.
N-(9-(Methoxyimino)-9H-xanthen-1-yl)-4-nitrobenzenesulfonamide (5m)
32.3 mg, 44 % yield. Pale yellow solid; mp: 167-168 oC; 1H NMR
(400 MHz, CDCl3) δ 11.99 (br, 1H), 8.62 (dd, J = 8.3, 1.5 Hz, 1
H), 8.24–8.17 (m, 2H), 8.00–7.93 (m, 2H), 7.51–7.45 (m, 1H), 7.41
(dd, J = 8.1, 1.2 Hz, 1H), 7.33-7.29 (m, 1H), 7.20 (dd, J = 8.3, 1.
1 Hz, 1H), 7.18–7.11 (m, 1H), 6.96 (dd, J = 8.3, 1.2 Hz, 1H), 4.19
(s, 3H).13C NMR (100MHz, CDCl3) δ 152.3, 151.9, 149.6, 144.5, 1
43.2, 135.3, 132.4, 130.7, 130.4, 128.9, 127.9, 124.2, 123.7, 122.5,
116.7, 114.8, 114.6, 112.8, 108.1, 63.2. HRMS Calcd for C20H15N3
NaO6S [M+Na]+: 448.0579; Found: 448.0587.
2-methoxy-3-methyl-6-nitro-2H-indazole (4) the spectroscopic data of
the product matched those previously reported.11 21.2 mg, 51% yi
eld. Yellow solid; mp: 121-123 oC; 1H NMR (400 MHz, CDCl3) δ 8.
61 (d, J = 1.4 Hz, 1H), 7.90 (dd, J = 9.1, 1.4 Hz, 1H), 7.65 (d, J
= 9.1 Hz, 1H), 4.34 (s, 3H), 2.65 (s, 3H). Spectral data matched th
ose previously reported.11
N-(4-(Methoxyimino)chroman-5-yl)-4-nitrobenzenesulfonamide (5n) 46.
6 mg, 62 % yield. Pait solid; mp: 139-140oC; 1H NMR (400 MHz,
CDCl3) δ 11.53 (br, 1H), 8.30–8.23 (m, 2H), 8.05–7.95 (m, 2H), 7.2
1–7.10 (m, 2H), 6.60 (dd, J = 7.8, 1.6 Hz, 1H), 4.10 (t, J = 6.3 H
z, 2H), 4.08 (s, 3H), 2.88 (t, J = 6.3 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 157.8, 152.4, 150.1, 145.3, 136.8, 131.4, 128.5, 124.1, 1
13.4, 111.5, 106.5, 64.0, 62.9, 23.8. HRMS Calcd for C16H15N3NaO6
S [M+Na]+: 400.0579; Found: 400.0572.
N-(5-Amino-2-(1-(methoxyimino)ethyl)phenyl)-4-methylbenzenesulfona
mide (5) 58.6 mg, 88 % yield. Yellow solid; mp:151-152 oC.1H NM
R (400 MHz, CDCl3) δ 11.18 (br, 1H), 7.62 (d, J = 8.2 Hz, 2H), 7.
18 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.5 Hz, 1H), 6.93 (d, J = 2.2
Hz, 1H), 6.33 (dd, J = 8.5, 2.2 Hz, 1H), 4.00 (s, 3H), 3.90 (br, 2
H), 2.34 (s, 3H), 1.99 (s, 3H).13C NMR (100 MHz, CDCl3) δ 156.3,
147.8, 143.3, 137.5, 136.5, 129.8, 129.3, 127.1, 114.0, 110.2, 106.
5, 62.2, 21.4, 12.7. HRMS Calcd for C16H19N3NaO3S [M+Na]+: 356.
1045; Found: 356.1041.
N-(5-Fluoro-2-(1-(methoxyimino)ethyl)-4-nitrophenyl)-4-methylbenzenes
ulfonamide (5o) 42.7 mg, 53 % yield. Pale yellow solid; mp: 172-17
3
oC; 1H NMR (400 MHz, CDCl3) δ 12.00 (br, 1H), 8.21 (d, J = 8.
0 Hz, 1H), 7.81–7.74 (m, 2H), 7.49 (d, J-F = 13.1 Hz, 1H), 7.31 (d,
J = 8.0 Hz, 2H), 4.12 (s, 3H), 2.41 (s, 3H), 2.29 (s, 3H).13C NMR
(100 MHz, CDCl3) δ 154.6, 154.2, 144.5, 143.1, 135.3, 129.6, 126.
8, 126.7, 116.9, 106.2 (d, J-F = 26.6 Hz), 99.5, 62.6, 21.1, 12.5.19
F NMR (400 MHz, CDCl3) δ -111.54(s). HRMS Calcd for C16H16FN3
NaO5S [M+Na]+: 404.0692; Found: 404.0704.
1-(2-amino-4-nitrophenyl)ethanone O-methyl oxime (6) 35.2 mg, 84 %
yield. Orange solid; mp: 115-116 oC. 1H NMR (400 MHz, CDCl3) δ 7.51
(d, J = 1.8 Hz, 1H), 7.49 – 7.43 (m, 2H), 6.00 (s, 2H), 4.02 (s, 3H), 2.29
(s, 3H). 13C NMR (101 MHz, CDCl3) δ 155.8, 147.9, 146.6, 129.4, 122.7,
N-(5-Chloro-2-(1-(methoxyimino)ethyl)-4-nitrophenyl)-4-methylbenzenes
110.7, 110.5, 62.3, 13.0. HRMS Calcd
232.0698; Found: 232.0704.
for C9H11N3NaO3 [M+Na]+:
ulfonamide (5p) 49.9 mg, 65 % yield. Pale yellow solid; mp: 206-20
7
oC; 1H NMR (400 MHz, CDCl3) δ 11.74 (br, 1H), 8.08 (s, 1H), 7.
76 (s, 1H), 7.76 (dd, J = 6.4, 2H), 7.30 (d, J = 8.0 Hz, 2H), 4.13
(s, 3H), 2.41 (s, 3H), 2.25 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 1
54.9, 144.8, 141.4, 141.0, 135.8, 130.1, 129.4, 127.3, 126.7, 120.5,
120.3, 63.2, 21.6, 12.9. HRMS Calcd for C16H16ClN3NaO5S [M+Na]+:
420.0397; Found: 420.0406.
N-(2-Acetyl-5-nitrophenyl)-4-nitrobenzenesulfonamide (7) 63.4 mg, 8
7 % yield. Pale yellow solid; mp: 55-56 oC; 1H NMR (400 MHz, C
DCl3) δ 11.74 (br, 1H), 8.55 (d, J = 2.2 Hz, 1H), 8.38–8.30 (m, 2
H), 8.17–8.11 (m, 2H), 8.04 (d, J = 8.7 Hz, 1H), 7.92 (dd, J = 8.7,
2.2 Hz, 1H), 2.69 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 201.7, 1
50.9, 150.6, 144.6, 140.4, 133.3, 128.7, 125.2, 124.8, 117.3, 113.3,
28.7. HRMS Calcd for C14H17N3NaO7S [M+Na]+: 388.0215; Found:
388.0223.
N-(5-Bromo-2-(1-(methoxyimino)ethyl)-4-nitrophenyl)-4-methylbenzenes
ulfonamide (5q) 44.9 mg, 61 % yield. Pale yellow solid; mp: 217-21
9
oC; 1H NMR (400 MHz, CDCl3) δ 11.68 (br, 1H), 8.05 (s, 1H), 7.
97 (s, 1H), 7.76 (d, J = 8.3 Hz, 2H), 7.30 (d, J = 8.3 Hz, 2H), 4.1
3 (s, 3H), 2.41 (s, 3H), 2.24 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
154.9, 144.8, 143.4, 140.8, 135.8, 130.0, 127.3, 126.6, 123.9, 120.
9, 116.8, 63.2, 21.6, 12.8. HRMS Calcd for C16H16BrN3NaO5S [M+N
a]+: 463.9892; Found: 463.9899.
Acknowledgments
We gratefully acknowledge financial support from the Natural
Science Foundation of China (Nos. 21772139, 21572149). The
Major Basic Research Project of
the natural Science
N-(2-(1-(Methoxyimino)ethyl)-5-methyl-4-nitrophenyl)-4-methylbenzenes
Foundation of Jiangsu Higher Education Institutions (No.
15KJA150006 and 17 KJA150006), Jiangsu Province Natural
Science Found for Distinguished Young Scholars (No.
BK2018g0041), Project of Scientific and Technologic
Infrasracture of SuZhou (No. SZS2018201708) and the PAPD
Project.
ulfonamide (5r) 44.7 mg, 56 % yield. Pale yellow solid; mp: 226-22
7
oC; 1H NMR (400 MHz, CDCl3) δ 11.66 (br, 1H), 8.21 (s, 1H), 7.
86–7.70 (m, 2H), 7.58 (s, 1H), 7.32 (m, 2H), 4.16 (s, 3H), 2.64 (s,
3H), 2.44 (s, 3H), 2.29 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 15
5.3, 144.4, 143.3, 140.7, 136.6, 136.2, 129.8, 127.2, 125.9, 121.8,
120.2, 62.9, 21.5, 21.4, 12.8. HRMS Calcd for C17H20N3O5S [M+H]
+: 378.1124; Found: 378.1115.
6
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10.1002/ejoc.201901517
European Journal of Organic Chemistry
2002, 8, 1563; c) J. L. Liang，S. X. Yuan, J. L. Huang, W. Y. Yu，C. M. Che,
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KeyWords: rhodium • potassium acetate • ketoximes• 4-
nitrobenzenesulfonamide • amination
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This article is protected by copyright. All rights reserved.

10.1002/ejoc.201901517
European Journal of Organic Chemistry
FULL PAPER
A method to achieve rhodium(III)-
catalyzed, potassium acetate enabl
ed intermolecular C-H amination o
f ketoximes using various benzene
sulfonamide, especially 4-nitrobenz
enesulfonamide is reported.
Various aryl ketoximes substituted with electron-withdrawing functional groups were all
well tolerated and produced the corresponding products in moderate to good yields. A
preliminary mechanistic study revealed that potassium acetate is essential to realizing
intermolecular amination.
Lingling Liu,[a] Ning Wang,[a] Chenyan
g Dai,[a] Yi Han,[a] Shan Yang,[a] Zhibi
n Huang,*[a] Yingsheng Zhao*[a]
Page No. – Page No.
Rh(III)-catalyzed, potassium acetate
enabled, ketoxime-assisted direct
amination of aromatic ketoximes
4-nitrobenzenesulfonamide • Construction of C-N
8
This article is protected by copyright. All rights reserved.