Iridium(III)-Catalyzed Directed ortho-C(sp2)–H Amidation of Arenes with Sulfonamides

Article abstract of DOI:10.1002/ejoc.201800192

An iridium(III)-catalyzed ortho-C(sp²)–H amidation of O-methyl ketoximes with sulfonamides has been accomplished under mild conditions. This protocol can be successfully applied to a broad scope of oxime substrates and works well with a range of aryl- and alkylsulfonamides.

Full text of DOI:10.1002/ejoc.201800192

A Journal of
Accepted Article
Title: Iridium(III)-Catalyzed Directed ortho-C(sp2)-H Amidation of
Arenes with Sulfonamides
Authors: Wei Zhang, Darun Yang, Wengui Wang, Shoufeng Wang, and
Huaiqing Zhao
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201800192
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10.1002/ejoc.201800192
European Journal of Organic Chemistry
COMMUNICATION
Iridium(III)-Catalyzed Directed ortho-C(sp2)–H Amidation of
Arenes with Sulfonamides
Wei Zhang,[a] Darun Yang,[a] Wengui Wang,[b] Shoufeng Wang,[b] Huaiqing Zhao*[a]
Abstract: An iridium(III)-catalyzed ortho-C(sp2)–H amidation of O-
methyl ketoximes with sulfonamides has been accomplished under
mild conditions. This protocol can be successfully applied to a broad
scope of oxime substrates and works well with a range of aryl and
alkyl sulfonamides.
products are difficult to generate other valuable compounds.[7h]
Our continuous research efforts have been devoted to
developing an efficient catalytic system for expanding the scope
of arenes and amines. Inspired by the importance of
sulfonamides containing oxime groups, we wish to report an
Ir(III) catalyzed direct C–H bond amidation of O-methyl
ketoximes with sulfonamides. The oxime group is widely
employed as an efficient directing group in the C–H bond
functionalization reactions. [2k], [9] Moreover, the oxime group of
products can be easily removed to recover the carbonyl group
for further structural modifications, or be transformed to other
functional groups.[10]
Introduction
C–H bond is the common functional group in organic molecules
but is relatively difficult to transform into other valuable functional
groups due to its inert activity.[1] In the past decades, transition-
metal catalyst has been extensively utilized to explore the C–H
functionalization.[2] As a streamline synthetic route, this strategy
has been explored to construct the ubiquitous C–N bonds in
natural products, pharmaceuticals, agrochemicals, and organic
materials.[3] Meanwhile, this protocol is an alternative to the most
representative Buchwald-Hartwig amination reactions[4] and the
Ullmann-Goldberg coupling reactions[5] and avoids the pre-
functionalization of arenes in the form of halides or
pseudohalides. The direct transition-metal catalyzed C–H
aminations of arenes with free amines is a paramount and
promising synthetic approach for molecular construction with
high atom- and economy-step.[6] Although there has been
significant progress in this area, this strategy is still limited to the
application to specific substrates which generally contain a
functional group as the directing group assisting C–H bond
activation and controlling regioselectivity.[7]
The sulfonamide has been demonstrated to be an important
functional group in organic compounds and widely reside within
pharmaceuticals, natural and non-natural compounds (Scheme
1).[8] Moreover, the sulfonamide as a desirable and effective
nitrogen source has been usually utilized in the construction of
C–N bond.[6c], [6e] Recently, we had explored a mild and efficient
rhodium(III)-catalyzed amidation of 2-arylpyridines with
sulfonamides. However, the substrates in this catalytic system
are limited to 2-arylpyridines and sulfonamides, and their
Scheme 1. Antiobesity agents (I) and anti-inflammatory agents (II).
Results and Discussion
Recent progress in the Ir-complexes catalyzed C–H bond
functionalization has provided valuable information for our
exploration of the amidation.[11], [12] At the outset of our research,
we selected the reaction between acetophenone O-methyl
oxime (1a) and p-toluenesulfonamide (2a) as a model reaction.
In light of our previous investigation about C–H bond amination,
the initial conditions of [Cp*IrCl2]2 (2.5 mol-%), AgSbF6 (10 mol-
%), PhI(OAc)2 (1.5 equiv.) and 1,2-dichloroethane (DCE) at 60
oC were used under nitrogen atmosphere (Table 1, entry 1).
However, there was no desired product under this catalytic
system.
Subsequently,
substituting
PhI(OAc)2
with
PhI(CF3COO)2 as oxidant in this reaction also yielded no desired
product (Table 1, entry 2). Satisfactorily, the desired product was
observed in 30% yield when silver carbonate was used as
oxidant in the catalytic system (Table 1, entry 3). Encouraged by
this result, other metallic salts were tested as oxidants in this
transformation, and silver acetate was found to afford the
product in 65% yield (Table 1, entries 3-5). The effect of solvent
was considered, and there was no significant improvement in
product yield (Table 1, entries 6-9). By increasing the amount of
AgOAc to 2.5 equivalents, the product yield increased to 74%
(Table 1, entry 8). The evident improvement emerged when the
reaction was occurred in dichloromethane (DCM) (Table 1, entry
9). Further investigations revealed that this reaction could be
[a]
W. Zhang, D. Yang, H. Zhao
Key Laboratory of Interfacial Reaction & Sensing Analysis in
Universities of Shandong, School of Chemistry and Chemical
Engineering
University of Jinan
No. 336, West Road of Nan Xinzhuang Jinan, Shandong, 250022,
China
E-mail: chm_zhaohq@ujn.edu.cn.
http://chem.ujn.edu.cn/showjiaoshi.asp?jiaoshiid=184
W. Wang, S. Wang
[b]
Shandong Provincial Key Laboratory of Fluorine Chemistry and
Chemical Materials, School of Chemistry and Chemical Engineering
University of Jinan
No. 336, West Road of Nan Xinzhuang Jinan, Shandong, 250022,
China
o
implemented under a milder condition (60 C) with a good yield
(Table 1, entries 9-11). The control experiments showed that the
Ir(III) catalyst and AgNTf2 are pivotal to achieving this
transformation (Table 1, entries 14, 15).
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201800192
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COMMUNICATION
Table 2. Ir-catalyzed amidation of different oximes [
a]
Table 1. Optimization of reaction conditions for Ir(III) catalyzed C-H bond
amidation [a]
Entry
Oxidant [equiv.]
Solvent
Temp.[oC]
Yield [%] [b]
1
PhI(OAc)2 (1.5)
PhI(CF3COO)2 (1.5)
Ag2CO3 (1.0)
Cu(OAc)2 (1.0)
AgOAc (2.0)
AgOAc (2.0)
AgOAc (2.0)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
AgOAc (2.5)
DCE
60
60
60
60
60
60
60
60
60
40
80
60
60
60
60
0
2
DCE
0
3
DCE
30
<5
65
13
0
4
DCE
5
DCE
6
1,4-Dioxane
DMF
7
8
DCE
74
90
85
91
81
13
0
9
DCM
DCM
DCM
DCM
DCM
DCM
DCM
10
11
12 [c]
13 [d]
14 [e]
15 [f]
[a] Reaction conditions: 1 (0.2 mmol), 2a (0.4 mmol), [Cp*IrCl2]2 (2.5 mol-%),
AgNTf2 (10 mol-%), AgOAc (2.5 equiv.), DCM (2 mL), 24 h, isolated yield.
[b] The ratio of 1 to 2a is 1:3. [c] DCE as a solvent.
product or the yield of the corresponding product was of no
immediate value of the utility in synthesis.
Employing acetophenone O-methyl oxime (1a) as a substrate,
the scope of amides was examined using the established
conditions (Table 1, entry 9). As shown in Table 3, different
arylsulfonamides containing either electron-donating or
withdrawing groups furnished the corresponding products in
good or excellent yields (4b-4i). We noted that the desired
products slightly decreased when the substitute such as Me, F
and Cl were installed at 2-position of the arylsulfoamide (4c, 4d
and 4g). However, 4-nitrobenzenesulfonamide afforded the
desired product in only 31% yield under the standard conditions.
Gratifyingly, the desired product (4j) was obtained in excellent
yield by increasing the reaction temperature to 90 oC. This
protocol is also applicable to alkyl-substituted sulfonamides (4k-
4n). But the reaction conditions were slightly modified such as
prolonging the reaction time or increasing the temperature. We
also tried to investigate other amides such as alkylamides,
benzamides, and anilines which did not react with acetophenone
O-methyl oxime under the optimal conditions. The acidity of the
<5
[a] Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), [Cp*IrCl2]2 (2.5 mol-%),
[b]
[c]
AgNTf2 (10 mol-%), oxidant, solvent (2 mL), N2, 24 h. Isolated yield. The
[d]
ratio of 1a to 2a is 1:1.5.
The ratio of 1a to 2a is 2:1. [e] In the absence of
[Cp*IrCl2]2. [f] In the absence of AgNTf2.
To evaluate the effectiveness of the optimal protocol (Table 1,
entry 9), we first investigated the scope of O-methyl ketoximes.
As shown in Table 2, various O-methyl ketoximes bearing an
electron-donating group such as a methyl or a methoxyl group
afforded the desired products in moderate to excellent yields
(3b-3f). Notably, this transformation was sensitive to steric and
electronic factor. The corresponding products obviously
decreased when the substitute was installed at 2- or 3-postion of
O-methyl ketoximes (3b, 3c, 3e). Substrates bearing electron-
withdrawing groups such as F, Cl, Br, COOMe and CF3 groups
furnished excellent yields (3g-3l). The halogen and ester groups
can also be further modified to transfer other functional groups.
The amidation of benzophenone and α-tetraloneoxime O-methyl
oxime produced the desired product 3m and 3n in 93% and 56%
yields, respectively. We also found that the optimal conditions
were applicable to the aromatic heterocyclic O-methyl ketoxime.
The thiophene with an oxime group as the directing group was
successfully amidated in 59% yield (3o). Other heterocyclic O-
methyl ketoximes were also tried, but there was no desired
N-H bond is considered to be
transformation.[7h]
a vital factor for this
To probe whether C–H bond activation involves the rate-
limiting step in this catalytic system, the kinetic isotope effect
(KIE) of acetophenone O-methyl oxime was investigated in both
parallel and one-vessel measurements. The KIE values of 1.04
in parallel reaction and 1.22 in one-vessel competition reaction
indicated that C–H bond activation is not possible rate-limiting
step in this catalytic cycle (Scheme 2).[13] The intermolecular
competition experiment between differently substituted O-methyl
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COMMUNICATION
Table 3. Ir-catalyzed amidation of different amides [a]
Scheme 3. Intermolecular competition experiment.
from the relevant Ir(III) catalyst precursor, which cleaves C–H
bond of 1a to generate a five-membered iridacycle intermediate
II. Subsequently, the amide coordinates to Ir(III) center via the N
atom producing intermediate III, which is likely oxidized to form
an Ir(V)-nitrenoid intermediate IV by silver acetate.[16] The
intermediate IV then undergoes reductive elimination to form C–
N bond Ir(III) species V. Finally, the six-membered iridacycle is
protonated by the acid formed in situ, delivering the desired
product.
[a]
Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), [Cp*IrCl2]2 (2.5 mol-%),
[b]
AgNTf2 (10 mol-%), AgOAc (2.5 equiv.), DCM (2 mL), 24 h, isolated yield.
Reaction temperature is 90 oC. [c] Reaction time：48 h.
ketoximes 1 was also carried out, which revealed electron-
deficient O-methyl ketoximes to be converted faster (Scheme 3).
Meanwhile, there was no desired product when the
stoichiometric [Cp*IrCl2]2 was added to the reaction without
oxidant. Although more comprehensive mechanistic studies are
required to confirm the rate determining step of this catalytic
cycle and understand the process of C–N bond forming, these
will need more efforts in future. Now based on the above
experiments and the related results reported by others, a
plausible catalytic mechanism is proposed in Scheme 4. [7j], [7l], [14],
[15] Firstly, a highly electrophilic Ir(III) species I formes in situ
Scheme 4. Proposed mechanism of amidation
Conclusions
To summarize, we have accomplished the Ir(III)-catalyzed ortho-
C(sp2)–H amidation of O-methyl ketoximes with sulfonamides
under mild conditions for the first time. This efficient method
enables a broad scope of O-methyl ketoximes to react with both
aromatic and aliphatic sulfonamides with good functional group
tolerance and selectivity in moderate to excellent yields. This
approach is a complement to the existing methods for the
construction of sulfonamides containing oxime groups. We
expect that future efforts will be spent on expanding the scope of
simple arenes and amines, and apply this protocol to synthesize
important amidated compounds such as biological and natural
products.
Scheme 2. Deuteration experiments
Experimental Section
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COMMUNICATION
General comments: All reagents were purchased and used without
further purification. DCM, DCE and DMF were both distilled from CaH2
under nitrogen and stored under nitrogen. 1,4-Dioxane was distilled from
sodium and benzophenone under nitrogen and stored over 4Ǻ molecular
sieves under nitrogen. 1H NMR and 13C NMR data were obtained on a
Bruker (400 or 600 MHz) nuclear resonance spectrometer with CDCl3 as
solvent and tetramethylsilane (TMS) as internal standard. Chemical shifts
were reported in units (ppm) by assigning TMS resonance in the 1H NMR
spectra as 0.00 ppm (chloroform, 7.26 ppm). Data were reported as
follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet and
m = multiplet), coupling constant (J values) in Hz and integration.
Chemical shifts for 13C NMR spectra were recorded in ppm from
tetramethylsilane using the central peak of CDCl3 (77.0 ppm) as the
internal standard. Flash column chromatography was performed using
300 - 400 mesh silica with the indicated solvent system according to
standard techniques. Analytical thin layer chromatography (TLC) was
performed on pre-coated, glass-backed silica gel plates. The yields of
products reported are the isolated yields and the average of two runs.
(s, 1H), 7.58 (d, J = 8.3 Hz, 2H), 7.45 (d, J = 0.8 Hz, 1H), 7.17 (d, J = 8.0
Hz, 3H), 6.88 (d, J = 8.1, 1.0 Hz, 1H), 4.04 (s, 3H), 2.35 (s, 3H), 2.31 (s,
3H), 1.97 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 155.9, 143.4, 140.2,
136.5, 135.7, 129.4, 128.3, 127.2, 125.0, 122.4, 121.8, 62.5, 21.5, 21.4,
13.0. HRMS (ESI) m/z calcd for C17H20N2O3S [M+H]+, 333.1267; found,
333.1263.
N-[2-(1-methoxyimino)ethyl-3-methoxyl]phenyl-4-
methylbenzsulfamide (3e). White solid; m.p. 104-106 oC; (0.034 g, 50%
yield); (Rf = 0.20, petroleum ether/ ethyl acetate, 25:3). 1H NMR (600
MHz, CDCl3) δ 9.9 (s, 1H), 7.59 (d, J = 8.9 Hz, 1H), 7.44 (d, J = 8.3 Hz,
2H), 7.14 (d, J = 8.0 Hz, 2H), 6.85 (dd, J = 8.9, 2.3 Hz, 1H), 6.74 (d, J =
2.9 Hz, 1H), 4.02 (s, 3H), 3.78 (s, 3H), 2.34 (s, 3H) 1.78 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 156.9, 155.1, 143.2, 136.1, 129.2, 128.1, 128.0,
127.2, 126.0, 114.5, 114.0, 62.6, 55.5, 21.5, 13.2. HRMS (ESI) m/z calcd
for C17H20N2O4S [M+H]+,349.1217; found, 349.1221.
N-[2-(1-methoxyimino)ethyl-4-methoxyl]phenyl-4-
methylbenzsulfamide (3f). White solid; m.p. 108-110 oC; (0.064 g, 91%
yield); (Rf = 0.25, petroleum ether/ ethyl acetate, 25:3). 1H NMR (600
MHz, CDCl3) δ 11.16 (s, 1H), 7.63 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.8 Hz,
1H), 7.20 (s, 1H), 7.18 (d, J = 2.5 Hz, 2H), 6.57 (dd, J = 8.8, 2.6 Hz, 1H),
4.04 (s, 3H), 3.78 (s, 3H), 2.35 (s, 3H), 2.03 (s, 3H). 13C NMR (151 MHz,
CDCl3) δ 160.3, 156.0, 143.5, 137.7, 136.5, 129.7, 129.4, 127.2, 116.4,
109.9, 105.8, 62.4, 55.4, 21.5 13.0. HRMS (ESI) m/z calcd for
C17H20N2O4S [M+H]+, 349.1217; found, 349.1225.
Typical Procedure for Ir(III)-Catalyzed amidation of O-methyl ketoximes:
In a glovebox, the Schlenk tube equipped with a stir bar was charged
with [Cp*IrCl2]2 (0.005 mmol, 2.5 mol-%), AgNTf2 (0.02 mmol, 10 mol-%),
amide (0.4 mmol, 2.0 equiv.), AgOAc (0.5 mmol, 2.5 equiv.). The tube
was fitted with a rubber septum and removed out of the glovebox. The O-
methyl ketoxime (0.2 mmol) was added to the Schlenk tube through the
rubber septum using a syringe. Then solvent (DCM, 2 mL) was added
using a syringe. The rubber septum was replaced with a Teflon screwcap
under nitrogen flow. The mixture was stirred and heated for 24 h. After
cooling, the reaction mixture was diluted with ethyl acetate (10 mL) and
filtered through a pad of silica gel, followed by washing the pad of the
silica gel with the same solvent (20 mL). The organic phase was
concentrated under reduced pressure. The residue was then purified by
chromatography on silica gel to provide the corresponding product.
N-[2-(1-methoxyimino)ethyl-4-fluoro]phenyl-4-methylbenzsulfamide
(3g). White solid; m.p. 176-178 oC; (0.059 g, 87% yield); (Rf = 0.28,
1
petroleum ether/ ethyl acetate, 25:3) H NMR (400 MHz, CDCl3) δ 11.21
(s, 1H), 7.65 (d, J = 8.2 Hz, 2H), 7.36 (dd, J = 10.6, 2.5 Hz, 1H), 7.30 –
7.26 (m, 1H), 7.21 (d, J = 8.1 Hz, 2H), 6.76 – 6.72 (m, 1H), 4.06 (s, 3H),
2.36 (s, 3H), 2.08 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 162.8 (d, J = 250
Hz),155.6, 143.8, 138.1 (d, J = 11.2 Hz), 136.4, 130.2 (d, J = 9.9 Hz),
129.6, 127.2, 13C NMR (101 MHz, CDCl3) δ 162.77 (d, J = 250.0 Hz),
110.5 (d, J = 21.8 Hz), 107.7 (d, J = 26.5 Hz), 62.6, 21.5, 13.1. HRMS
(ESI) m/z calcd for C16H17FN2O3S [M+H]+, 337.1017; found, 337.1023.
N-[2-(1-methoxyimino)ethyl]phenyl-4-methylbenzsulfamide (3a).[17]
White solid; m.p. 127-129 oC; (0.057 g, 90% yield); (Rf = 0.31, petroleum
ether/ ethyl acetate, 25:3); 1H NMR (400 MHz, CDCl3) δ 10.78 (s, 1H),
7.65 (dd, J = 8.2, 1.0 Hz, 1H), 7.61 (s, 1H), 7.58 (s, 1H), 7.33-7.28 (m,
2H), 7.19 (d, J = 8.1 Hz, 2H), 7.10 (td, J = 7.4, 1.2 Hz, 1H), 4.07 (s, 3H),
2.36 (s, 3H), 2.01 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 155.9, 143.5,
136.5, 135.8, 129.7, 129.4, 128.5, 127.2, 124.5, 124.1, 121.9, 62.6, 21.5,
13.2.
N-[2-(1-methoxyimino)ethyl-4-chloro]phenyl-4-methylbenzsulfamide
(3h). White solid; m.p. 150-151 oC; (0.064 g, 90% yield); (Rf = 0.25,
1
petroleum ether/ ethyl acetate, 25:3) H NMR (400 MHz, CDCl3) δ 11.03
(s, 1H), 7.65 – 7.64 (m, 2H), 7.62 (s, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.20 (s,
1H), 7.02 (dd, J = 8.6, 2.2 Hz, 1H), 4.06 (s, 3H), 2.36 (s, 3H), 2.04(s, 3H).
13C NMR (101 MHz, CDCl3) δ 155.5, 143.8, 137.2, 136.3, 135.5, 129.6,
129.5, 127.2, 123.9, 122.1, 120.8, 62.7, 21.5, 13.1. HRMS (ESI) m/z
calcd for C16H17ClN2O3S [M+H]+, 353.0721;found, 353.0710.
N-[2-(1-methoxyimino)ethyl-2-methyl]phenyl-4-methylbenzsulfamide
(3b). White solid; m.p. 93-95 oC; (0.031 g, 47% yield); (Rf = 0.18,
petroleum ether/ ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 7.68
(s, 1H), 7.56 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.2 Hz, 1H), 7.22 (s, 1H),
7.21-7.18 (m, 2H), 6.98 (d, J = 7.6 Hz, 1H), 3.98 (s, 3H), 2.36 (s, 3H),
2.16 (s, 3H), 1.54 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 154.7, 143.7,
136.9, 136.6, 133.6, 129.6, 129.5, 129.0, 127.7, 127.2, 121.0, 62.2, 21.5,
20.2, 16.4. HRMS (ESI) m/z calcd for C17H20N2O3S [M+H]+, 333.1267;
found, 333.1270.
N-[2-(1-methoxyimino)ethyl-4-bromo]phenyl-4-methylbenzsulfamide
(3i). White solid; m.p. 144-146 oC; (0.071 g, 89% yield); (Rf = 0.19,
petroleum ether/ ethyl acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 10.98
(s, 1H), 7.81 (d, J = 1.3 Hz, 1H), 7.6 (d, J = 8.3 Hz, 2H), 7.23-7.19 (m,
2H), 7.18-7.17 (m, 2H), 4.06 (s, 3H), 2.36 (s, 3H), 2.03 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 155.6, 143.8, 137.2, 136.3, 129.7, 129.6, 127.2,
126.9, 123.7, 123.6, 122.6, 62.7, 21.5, 13.0 HRMS (ESI) m/z calcd for
C16H17BrN2O3S [M+H]+, 397.0216; found, 397.0215.
N-[2-(1-methoxyimino)ethyl-3-methyl]phenyl-4-methylbenzsulfamide
(3c). White solid; m.p. 100-102 oC; (0.030 g, 46% yield); (Rf = 0.15,
1
petroleum ether/ ethyl acetate, 25:3). H NMR (600 MHz, CDCl3) δ 10.43
(s, 1H), 7.54 (d, J = 8.3 Hz, 3H), 7.17 (d, J = 8.3 Hz, 2H), 7.09–7.06 (m,
2H), 4.04 (s, 3H), 2.34 (s, 3H), 2.28 (s, 3H), 1.92 (s, 3H). 13CNMR 13C
NMR (151 MHz, CDCl3) δ 155.8, 143.3, 136.4, 134.0, 132.9, 130.4,
129.3, 128.9, 127.2, 125.2, 122.7, 62.6, 21.5, 20.9, 13.2. HRMS (ESI)
m/z calcd for C17H20N2O3S [M+H]+, 333.1267; found, 333.1274.
N-[2-(1-methoxyimino)ethyl-4-methylformate]phenyl-4-
methylbenzsulfamide (3j). White solid; m.p. 118-120 oC; (0.067 g, 90%
yield); (Rf = 0.21, petroleum ether/ ethyl acetate, 25:3). 1H NMR (400
MHz, CDCl3) δ 10.78 (s, 1H), 8.27 (d. J = 1.6 Hz, 1H), 7.73 (dd, J = 8.3,
1.7 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.3 Hz, 1H), 7.19 (d, J =
8.0 Hz, 2H), 4.08 (s, 3H), 3.92 (s, 3H), 2.35 (s, 3H), 2.03 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 166.0, 155.5, 143.7, 136.3, 136.0, 131.0,
129.5, 128.5, 127.9, 127.3, 124.8, 122.4, 62.9, 52.4, 21.5, 13.2. HRMS
(ESI) m/z calcd for C18H20N2O5S [M+H]+, 377.1166; found, 377.1156.
N-[2-(1-methoxyimino)ethyl-4-methyl]phenyl-4-methylbenzsulfamide
(3d). White solid; m.p. 118-120 oC; (0.060 g, 89% yield); (Rf = 0.32,
1
petroleum ether/ ethyl acetate, 25:3). H NMR (600 MHz, CDCl3) δ 10.77
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COMMUNICATION
N-[2-(1-methoxyimino)ethyl-3-trifluoromethyl]phenyl-4-
(m, 1H), 7.09-7.07 (m, 1H), 6.85-6.84 (m, 2H), 4.06 (s, 3H), 3.80 (s, 3H),
2.03 (s, 3H). 13C NMR (101MHz, CDCl3) δ 162.9, 156.0, 135.9, 131.1,
129.7, 129.3, 128.5, 124.5, 124.1, 121.8, 113.9, 62.6, 55.6, 13.2. HRMS
(ESI) m/z calcd for C16H18N2O4S [M+H]+, 335.1060; found, 335.1059.
methylbenzsulfamide (3k). White solid; m.p. 124-126 oC; (0.066 g, 85%
yield); (Rf = 0.14, petroleum ether/ ethyl acetate, 25:3). 1H NMR (600
MHz, CDCl3) δ 11.33 (s, 1H), 7.71 (d, J = 8.9 Hz, 2H), 7.66 (s, 1H), 7.58
(d, J = 1.1 Hz, 1H), 7.46 (dd, J = 8.6, 1.6 Hz, 1H), 7.23 (d, J = 8.1 Hz, 2H),
4.10 (s, 3H), 2.36 (s, 3H), 2.17 (s, 3H). 13C NMR (151 MHz, CDCl3) δ
155.3, 144.1, 139.3, 136.4, 129.8, 127.2, 126.5 (q, J = 3.6 Hz), 125.6 (q,
J = 3.8 Hz), 124.9, 124.7, 122.9, 122.8, 120.0, 62.9, 21.5, 13.0. HRMS
(ESI) m/z calcd for C17H17F3N2O3S [M+H]+, 387.0985; found, 387.0990.
N-[2-(1-methoxyimino)ethyl]phenyl-2-methylbenzsulfamide
(4c).
White solid; (0.052 g, 82% yield); m.p. 94-96 oC; (Rf = 0.23, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 11.21 (s, 1H),
8.01 (dd, J = 8.0, 1.1 Hz, 1H), 7.47 (dd, J = 8.3, 1.0 Hz, 1H), 7.40-7.37
(m, 1H), 7.36 (dd, J = 8.0, 1.4 Hz, 1H), 7.28 (d, J = 7.50, 1H), 7.23 (d, J =
7.6, 1H), 7.20-7.17 (m, 1H), 7.03-7.01 (m, 1H), 4.06 (s, 3H) 2.62 (s, 3H),
2.17 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 156.4, 137.8, 137.3, 136.0,
132.9, 132.6, 130.0, 129.8, 128.6, 126.1, 122.9, 122.5, 118.9, 62.5, 20.0,
13.1. HRMS (ESI) calcd for C16H18N2O3S [M+H]+, 319.1111;found,
319.1120.
N-[2-(1-methoxyimino)ethyl-4-trifluoromethyl]phenyl-4-
methylbenzsulfamide (3l). White solid; m.p. 120-122 oC; (0.070 g, 90%
yield); (Rf = 0.45, petroleum ether/ ethyl acetate, 25:3). H NMR (600
MHz, CDCl3) δ 10.96 (s, 1H), 7.91 (d, J = 1.08 Hz, 1H) ,7.63 (d, J = 1.6
Hz, 2H), 7.42 (d, J = 8.3 Hz, 1H), 7.29 (dd, J = 8.3, 1.1 Hz, 1H), 7.21 (d, J
= 8.0 Hz, 2H), 4.10 (s, 3H), 2.36 (s, 3H), 2.08 (s, 3H) .13C NMR (151 MHz,
CDCl3) δ 155.3, 144.0, 136.3, 131.4 (q, J = 33.0 Hz), 129.6, 129.0, 127.2,
126.6, 124.3, 122.5, 120.2 (q, J = 3.7 Hz), 117.8 (q, J = 3.9 Hz), 62.9,
21.5, 13.2. HRMS (ESI) m/z calcd for C17H17F3N2O3S [M+H]+, 387.0985;
found, 387.0990.
1
N-[2-(1-methoxyimino)ethyl]phenyl-2-fluorobenzsulfamide
(4d).
White solid; (0.054 g, 83% yield); m.p. 110-112 oC; (Rf = 0.20, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 11.34 (s, 1H),
7.86-7.84 (m, 1H), 7.62 (dd, J = 8.3, 0.8 Hz, 1H), 7.50-7.49 (m, 1H), 7.35
(dd, J = 7.9, 1.38 Hz, 1H), 7.23-7.20 (m, 1H), 7.19-7.17 (m, 1H), 7.10 (t, J
= 8.9 Hz, 1H), 7.07-7.05 (m, 1H), 4.09 (s, 3H), 2.13 (s, 3H) 13C NMR (101
MHz, CDCl3) δ 158.9 (d, J = 256.7 Hz), 155.5, 135.4, 135.2 (d, J = 8.5
Hz), 130.9, 129.6, 128.5, 127.4 (d, J =13.6 Hz), 124.2 (d, J = 4.0 Hz),
123.8, 120.2, 117.0 (d, J = 21.1 Hz), 62.6, 13.1. HRMS (ESI) m/z calcd
for C15H15FN2O3S [M+H]+, 323.0860; found, 323.0859.
N-[2-(1-methoxyimino)ethyl-2-methyl]diphenyl-4-
methylbenzsulfamide (3m). White solid; m.p. 114-115 oC; (0.071 g,
93% yield); (Rf = 0.21, petroleum ether/ ethyl acetate, 25:3). 1H NMR
(400 MHz, CDCl3) δ 10.71 (s, 1H), 7.75-7.73 (m, 1H), 7.63 (d, J = 8.0 Hz,
2H), 7.39-7.37 (m, 3H), 7.33-7.28 (m, 1H), 7.19 (d, J = 8.0 Hz, 2H), 6.94-
6.90 (m, 1H), 6.85-6.83 (m, 2H), 6.69 (dd, J = 8.0, 1.3 Hz, 1H), 4.04 (s,
3H), 2.37 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 157.9, 143.6, 136.6,
136.4 ,132.5, 131.7, 129.9, 129.6, 129.2, 128.8, 128.1, 127.3,
124.8,124.0, 122.3, 63.1, 21.5. HRMS (ESI) m/z calcd for C21H20N2O3S
[M+H]+, 381.1267; found, 381.1265.
N-[2-(1-methoxyimino)ethyl]phenyl-3-fluorobenzsulfamide
(4e).
White solid; (0.058 g, 90% yield); m.p. 100-102 oC; (Rf = 0.21, petroleum
1
ether/ ethyl acetate, 25:3). H NMR (600 MHz, CDCl3) δ 10.87(s, 1H),
7.63 (dd, J = 8.2, 1.1 Hz, 1H), 7.50-7.48 (m, 1H), 7.41-7.40 (m, 1H), 7.39-
7.37 (m, 1H), 7.34-7.31 (m, 1H), 7.30-7.28 (m, 1H), 7.19-7.18 (m, 1H),
7.14-7.11 (m, 1H), 4.06 (s, 3H), 2.03 (s, 3H). 13C NMR (101 MHz, CDCl3)
δ 162.2 (d, J = 251.5 Hz), 156.0, 141.5 (d, J = 6.6 Hz), 135.3, 130.6 (d, J
= 7.7 Hz), 129.9, 128.6, 124.6 (d, J = 4.6 Hz), 123.0, 122.9 (d, J = 3.4
Hz), 122.0, 119.9 (d, J = 21.2 Hz), 114.5 (d, J = 24.5 Hz), 62.6, 13.1.
HRMS (ESI) m/z calcd for C15H15FN2O3S [M+H]+, 323.0860; found,
323.0866.
N-[2-(1-methoxyimino)ethyl-2-methyl]3,4-dihydrophenyl-4-
methylbenzsulfamide (3n). White solid; m.p. 96-98 oC; (0.036 g, 56%
yield); (Rf = 0.21, petroleum ether/ ethyl acetate, 25:3). 1H NMR (600
MHz, CDCl3) δ 11.44 (s, 1H), 7.63 (d, J = 12.3 Hz, 2H), 7.44 (d, J = 12.1
Hz, 1H), 7.18 (d, J = 12.00 Hz, 2H), 7.12 (t, J = 12.00 Hz, 1H), 6.81 (d, J
= 12.3 Hz, 1H), 4.06 (s, 3H), 2.63-2.59 (m, 4H), 2.35 (s, 3H) 1.67-1.61 (m,
2H). 13C NMR (101 Hz, CDCl3) δ 157.2, 143.4, 141.7, 137.0, 136.7,
129.4, 129.3, 127.3, 124.1, 118.5, 118.3, 62.7, 30.7, 25.1, 21.5, 20.7.
HRMS (ESI) m/z calcd for C18H20N2O3S [M+H]+, 345.1267; found,
345.1269.
N-[2-(1-methoxyimino)ethyl]phenyl-4-fluorobenzsulfamide (4f). White
o
solid; (0.057 g, 89% yield); m.p. 99-101 C; (Rf = 0.21, petroleum ether/
ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 10.83 (s, 1H), 7.72-
7.70 (m, 2H), 7.63 (dd, J = 8.2, 1.4 Hz, 1H), 7.33-7.28 (m, 1H), 7.27-7.24
(m, 1H), 7.13-7.08 (m, 1H), 7.08-7.05 (m, 2H), 4.06 (s, 3H), 2.03 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 165.0 (d, J = 254.9 Hz), 156.0, 135.5,
129.9, 129.8, 128.6, 124.6, 124.5, 122.0, 116.0 (d, J = 22.6 Hz), 115.9,
62.6, 13.1. HRMS (ESI) m/z calcd for C15H15FN2O3S [M+H]+, 323.0860;
found, 323.0865.
N-[2-(1-methoxyimino)ethyl-2-methyl]thienyl-4-methylbenzsulfamide
(3o). White solid; m.p. 119-121 oC; (0.038 g, 59% yield); (Rf = 0.31,
petroleumether/ ethyl acetate, 25:3). 1HNMR (400MHz, CDCl3) δ 10.13 (s,
1H), 7.66 (d, J = 8.3 Hz, 2H), 7.34 (d, J=5.4 Hz, 1H), 7.21 (d, J = 8.0 Hz,
2H), 7.17 (d, J = 5.5 Hz, 1H), 3.99 (s, 3H), 2.37 (s, 3H), 2.09 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 152.2, 143.7, 136.8, 135.1, 129.6, 127.0,
125.3, 122.4, 119.7, 62.5, 21.5, 14.9. HRMS (ESI) m/z calcd for
C14H16N2O3S2 [M+H]+, 325.0675; found, 325.0679.
N-[2-(1-methoxyimino)ethyl]phenyl-2-chlorobenzsulfamide
(4g).
White solid; (0.056 g, 82% yield); m.p. 88-90 oC; (Rf = 0.21, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 11.55 (s, 1H),
8.15 (dd, J = 8.2 ,1.4 Hz, 1H), 7.50 (dd, J = 8.3, 1.0 Hz, 1H), 7.44-7.43
(m, 1H), 7.43-7.41 (m, 1H), 7.37 (d, J = 1.3 Hz 1H), 7.36-7.35 (m, 1H),
7.18-7.15 (m, 1H), 7.02-6.99 (m, 1H), 4.08 (s, 3H), 2.21 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 155.8, 136.9, 135.5, 133.9, 132.0, 131.9, 129.7,
128.7, 126.9, 123.1, 122.9, 118.4, 62.6, 13.2. HRMS (ESI) m/z calcd for
C15H15ClN2O3S [M+H]+, 339.0565; found, 339.0570.
N-[2-(1-methoxyimino)ethyl]phenyl-benzsulfamide (4a). White solid;
(0.056 g, 93% yield); m.p. 105-107 oC; (Rf = 0.26, petroleum ether: ethyl
acetate, 25:3). 1HNMR (400MHz, CDCl3) δ 10.78 (s, 1H), 7.69 (d, J = 8.1
Hz, 2H), 7.65 (d, J = 8.2 Hz, 1H), 7.48 (t, J = 7.2 Hz, 1H), 7.38 (t, J = 8.2
Hz, 2H), 7.30-7.26 (m, 2H), 7.10 (t, J = 7.6 Hz, 1H), 4.06 (s, 3H), 1.98 (s,
3H). 13C NMR (101 MHz, CDCl3) δ 155.9, 139.4, 135.6, 132.7, 129.7,
128.8, 128.5, 127.1, 124.8, 124.4, 122.2, 62.6, 13.2. HRMS (ESI) m/z
calcd for C15H16N2O3S [M+H]+, 305.0954, found, 305.0961.
N-[2-(1-methoxyimino)ethyl]phenyl-4-chlorobenzsulfamide
(4h).
White solid; (0.061 g, 90% yield); m.p. 117-119 oC; (Rf = 0.47, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 10.86 (s, 1H),
7.63 (s, 1H), 7.62-7.60 (m, 2H), 7.38-7.37 (m, 1H), 7.35-7.34 (m, 1H),
7.32-7.28 (m, 2H), 7.13-7.09 (m, 1H), 4.06 (s, 3H), 2.03 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 156.0, 139.2, 137.9, 135.4, 129.8, 129.0, 128.6,
N-[2-(1-methoxyimino)ethyl]phenyl-4-methoxylbenzsulfamide (4b).
White solid; (0.065 g, 97% yield); m.p. 99-101 C; (Rf = 0.12, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 10.75 (s, 1H),
7.64-7.63 (m, 1H), 7.62 (s, 2H), 7.31 (dd, J = 7.9, 1.4 Hz, 1H), 7.28-7.24
o
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201800192
European Journal of Organic Chemistry
COMMUNICATION
128.5, 124.6, 124.5, 122.0, 62.7, 13.1. HRMS (ESI) m/z calcd for
C15H15ClN2O3S [M+H]+, 339.0565; found, 339.0585.
ZR2016BQ31), National Natural Science Foundation of China
(21302184) and University of Jinan is greatly appreciated.
N-[2-(1-methoxyimino)ethyl]phenyl-4-trifluoromethylbenzsulfamide
(4i). White solid; (0.063 g, 85% yield); m.p. 88-90 oC; (Rf = 0.19,
petroleum ether/ ethyl acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 10.92
(s, 1H), 7.81 (d, J = 8.2 Hz, 2H), 7.66 (dd, J = 8.3, 1.2 Hz, 1H), 7.33-7.32
(m, 2H), 7.31-7.30 (m, 1H), 7.29 (s, 1H), 7.16-7.12 (m, 1H), 4.07 (s, 3H),
1.98 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 155.9, 142.8, 135.1, 134.3,
129.9, 128.6, 127.6, 125.9 (q, J = 3.7 Hz), 124.8, 124.7, 122.2, 121.7,
62.7, 13.1. HRMS (ESI) m/z calcd for C16H15F3N2O3S [M+H]+, 373.0828;
found, 373.0835.
Keywords: Iridium • Amidation • O-methyl ketoxime •
Sulfonamide •C–H functionalization
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G. Dyker, Handbook of C−H Transformations: Applications in Organic
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N-[2-(1-methoxyimino)ethyl]phenyl-4-nitrobenzsulfamide (4j). Yellow
solid; (0.064 g, 92% yield); m.p. 113-115 oC; (Rf = 0.19, petroleum ether/
ethyl acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 11.11 (s, 1H), 8.25-
8.22 (m, 2H), 7.89-7.87 (m, 2H), 7.64 (dd, J = 8.2, 1.0 Hz, 1H), 7.36-7.33
(m, 1H), 7.32-7.28 (m, 1H), 7.16-7.12 (m, 1H), 4.08 (s, 3H), 2.04 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 156.1, 150.0, 145.2, 135.0, 130.0, 128.8,
128.4, 124.9, 124.3, 124.0, 121.7, 62.8, 13.1. HRMS (ESI) m/z calcd for
C15H15N3O5S [M+H]+, 350.0805; found, 350.0807.
N-[2-(1-methoxyimino)ethyl]phenyl-benylmethanesulfonamide (4k).
White solid; (0.039 g, 62% yield); m.p. 101-103 oC; (Rf = 0.29, petroleum
ether/ ethyl acetate, 25:3). 1H NMR (600 MHz, CDCl3) δ 10.90 (s, 1H),
7.83 (dd, J = 8.3, 1.1 Hz, 1H), 7.48 (dd, J = 8.0, 1.5 Hz, 1H), 7.36-7.33
(m, 1H), 7.33-7.30 (m, 1H), 7.27-7.25 (m, 2H), 7.16-7.13 (m, 1H), 7.11-
7.09 (m, 2H), 4.33 (s, 2H), 3.63 (s, 3H), 2.21 (s, 3H). 13C NMR (101 MHz,
CDCl3) δ 155.7, 137.0, 130.7, 130.1, 128.8, 128.7, 128.6, 128.5, 123.3,
120.0, 118.5, 62.3, 57.3, 12.8. HRMS (ESI) m/z calcd for C16H18N2O3S
[M+H]+, 319.1111; found ,319.1115.
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N-[2-(1-methoxyimino)ethyl]phenyl-methylsulfonylamide (4l). Light
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7901-7902.
yellow liquid; (0.024 g, 50% yield); (Rf = 0.20, petroleum ether/ ethyl
1
acetate, 25:3). H NMR (400 MHz, CDCl3) δ 10.77 (s, 1H), 7.67 (dd, J =
8.2, 1.0 Hz, 1H), 7.50 (dd, J = 8.0, 1.4 Hz, 1H), 7.36-7.32 (m, 1H), 7.17-
7.13 (m, 1H), 4.04 (s, 3H), 2.98 (s, 3H), 2.31 (s, 3H) 13C NMR (101 MHz,
CDCl3) δ 156.4, 136.5, 130.1, 129.0, 123.7, 122.9, 119.6, 62.6, 39.6,
13.2. HRMS (ESI) calcd for C10H14N2O3S [M+H]+, 243.0798; found,
243.0807.
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G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054-3131.
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N-[2-(1-methoxyimino)ethyl]phenyl-isopropylsulfonamide (4m). Light
yellow liquid; (0.022 g, 40% yield); (Rf = 0.21, petroleum ether/ ethyl
1
acetate, 25:3). H NMR (400 MHz, CDCl3) δ 10.79 (s, 1H), 7.79 (dd, J =
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7453.
8.3, 1.1 Hz, 1H), 7.49 (dd, J = 8.0, 1.5 Hz,1H), 7.33-7.29 (m, 1H), 7.12-
7.09 (m, 1H), 4.03 (s, 3H), 3.32-3.24 (m, 1H), 2.31(s, 3H), 1.36-125 (m,
6H). 13C NMR (101 MHz, CDCl3) δ 156.5, 137.1, 130.1, 128.9, 123.0,
122.0, 118.8, 62.5, 52.2, 16.4, 13.1. HRMS (ESI) m/z calcd for
C12H18N2O3S [M+H]+, 271.1111; found, 271.1118.
N-[2-(1-methoxyimino)ethyl]phenyl-tert-butyl sulfonamide (4n). Light
yellow liquid; (0.019 g, 35% yield); (Rf = 0.21, petroleum ether/ ethyl
acetate, 25:3). 1H NMR (400 MHz, CDCl3) δ 10.60 (s, 1H), 7.86 (dd, J =
8.4, 1.0 Hz, 1H), 7.39 (dd, J = 8.0, 1.5 Hz, 1H), 7.22-7.19 (m, 1H), 7.02-
7.00 (m, 1H), 3.95 (s, 3H), 2.25 (s, 3H), 1.30 (s, 9H). 13C NMR (101 MHz,
CDCl3) δ 156.6, 138.4, 129.9, 128.6, 122.9, 121.8, 119.6, 62.5, 61.6,
24.6, 13.3. HRMS (ESI) m/z calcd for C13H20N2O3S [M+H]+, 285.1267;
found, 285.1273.
Acknowledgements
Financial support from Shandong Provincial Natural Science
Foundation,12231 China (ZR2016JL009, ZR2016HM44 and
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COMMUNICATION
C-H Amidation*
Wei Zhang, Darun Yang, Wengui Wang,
Shoufeng Wang, Huaiqing Zhao*
Page No. – Page No.
Iridium(III)-Catalyzed Directed ortho-
C(sp2)–H Amidation of Arenes with
Sulfonamides
Text for Table of Contents
A mild and efficient Cp*Ir(III)-catalyzed ortho-C(sp2)–H amidation of O-methyl ketoximes with
sulfonamides has been developed, furnishing the corresponding products in good yields.
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