Copper-catalyzed C-N coupling reaction of tosylhydrazones

Article abstract of DOI:10.1002/aoc.4483

Tosylhydrazones are a kind of labile and highly reactive compounds, which are apt to be transformed into reactive diazo compounds and then into extremely reactive carbenes under the basic condition. In order to fulfil the valuable C-N coupling reaction, diaryliodonium salts are evaluated and prove to be a class of efficient electrophiles. The reaction with ligand-free copper salt as catalyst shows a wide range of substrate scope. A plausible mechanism is proposed.

Full text of DOI:10.1002/aoc.4483

Received: 6 March 2018
DOI: 10.1002/aoc.4483
Revised: 30 April 2018
Accepted: 31 May 2018
F U L L P A P E R
Copper‐catalyzed C‐N coupling reaction of tosylhydrazones
Xufeng Wu1 | Lingyu Li1 | Wenlong Jiang1 | Lihong Zhou2 | Qingle Zeng1
1 College of Materials, Chemistry &
Tosylhydrazones are a kind of labile and highly reactive compounds, which are
apt to be transformed into reactive diazo compounds and then into extremely
reactive carbenes under the basic condition. In order to fulfil the valuable
C‐N coupling reaction, diaryliodonium salts are evaluated and prove to be a
class of efficient electrophiles. The reaction with ligand‐free copper salt as cat-
alyst shows a wide range of substrate scope. A plausible mechanism is
proposed.
Chemical Engineering, State Key
Laboratory of Geohazard Prevention and
Geoenvironment Protection, Chengdu
University of Technology, 1#, Dongsanlu,
Erxianqiao, Chengdu 610059 Sichuan,
China
2 College of Environment and Ecology,
Chengdu University of Technology, 1#,
Dongsanlu, Erxianqiao, Chengdu 610059
Sichuan, China
KEYWORDS
Correspondence
C‐N coupling, copper catalysis, diaryliodonium salts, tosylhydrazones
Qingle Zeng, State Key Laboratory of
Geohazard Prevention and
Geoenvironment Protection, Chengdu
University of Technology, College of
Materials, Chemistry & Chemical
Engineering, 1#, Dongsanlu, Erxianqiao,
Chengdu 610059, China.
Email: qinglezeng@hotmail.com;
qlzeng@cdut.edu.cn
Funding information
Chengdu Science and Technology Bureau,
Grant/Award Number: 2015‐HM01‐00362‐
SF; Department of Science and Technol-
ogy of Sichuan Province, Grant/Award
Number: 2016HH0074; the State Key
Laboratory of Geohazard Prevention and
Geoenvironment Protection Independent
Research Project, Grant/Award Number:
SKLGP2016Z004
1 | INTRODUCTION
polysubstituted olefins[11–19] and multi‐arylmethanes[20]
with excellent structural diversities (Figure 1).
Tosylhydrazones are a class of useful organic reagents
with high reactivities.[1–3] They are used in synthesis of
alkenes with two name reactions, such as Shapiro reac-
tion[4–7] and the Bamford‐Stevens reaction.[8–10] Recently
tosylhydrazones have been found to be applied in more
and more new organic reactions.[11,12] Especially, it is
found that tosylhydrazones are a new kind of reagents
in palladium‐catalyzed coupling reactions with aryl
halides, sulfonates or boronic acids for synthesis of
Highly reactive and labile tosylhydrazones under
basic catalytic conditions make their C‐N coupling
reaction become an unresolved problem, although the
C‐N coupling reaction has achieved great progress.[21–27]
Inspired by our recent study of diaryliodonium salts and
amino acid amides,[28] we thought that diaryliodonium
salts may act as a class of suitable electrophiles for the
C‐N coupling reaction. As we known, diaryliodonium
salts are a kind of highly electron‐deficient aromatic
Appl Organometal Chem. 2018;e4483.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4483

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WU ET AL.
compounds with mildness, nontoxicity, stability and facile
preparation, and they have been widely applied in organic
synthesis.[29–32] As our on‐going study on C‐N cross cou-
pling reactions,[28–37] we planned to explore the reaction
of diaryliodonium salts and tosylhydrazones (Figure 1).
The C‐N coupling product sulfonamides are widely
applied in pharmaceuticals,[38] bioactive compounds,[39,40]
dyes and herbicides.[41,42] As an important buiding block
of drugs, it has been developing for decades.[43–45] The
traditional sulfonamide drugs are obtained through the
reaction of amine and sulfonyl chloride.[46] But sulfonyl
chloride is troublesome in the reaction process,
because it is corrosive, hydrolysable easily and hazard-
ous.[47,48] Taking into account these unfavorable factors,
a mild and highly efficient method to synthesize sulfon-
amides is highly concerned.
angiogenic drug; and WXL‐1 is a potent antimicrobial
agent, newbouldine and neuro‐transmitter inhibitors
(Figure 2).[49–51]
2 | EXPERIMENTAL
2.1 | General
All reactions were carried out under argon atmosphere in
dried glassware. The glassware used were dried in an
electric oven at 120°C. Chemicals were purchased from
Aladdin, Adamas, Aldrich, Alfa Aesar, and Kelong
Chemical Company, and used without further treatment.
Petroleum ether refers to the fraction boiling in the
1
60–90°C range. H NMR spectra were determined on a
Bruker Avance 300 MHz instrument or on a Bruker
Avance III 400 MHz instrument. 1H NMR data are
reported in δ units (ppm), and were measured relative
to the signals for residual chloroform (7.26 ppm), DMSO
(2.50 ppm) or acetone (2.05 ppm) in the deuterated
solvent, unless otherwise stated. 13C NMR spectra are
reported in (ppm) relative to deuterochloroform
(77.2 ppm), DMSO‐d6 (39.5 ppm) or acetone‐d6
(206.7 ppm for C=O) unless otherwise stated, and all
Sulfonamides and indazoles are important building
blocks for pharmaceuticals and bioactive compounds. For
example, ionidamine is an anticancer drug; YC‐1 is
reported to exhibit anticancer activity; YD‐3 is an
1
were obtained with H decoupling. High‐resolution mass
spectra were recorded on a Shimadzu LCMS‐IT‐TOF
instrument in the ESI mode. IR spectra were taken on a
Thermo Nicolet NEXUS 670 FTIR infrared spectrometer
using a Nicolet Omnic workstation.
2.2 | General procedure
To an oven‐dried 25 ml test tube with standard ground
joint equipped with a stir bar was added 0.5 mmol N‐
tosylhydrazones, 0.7 mmol diphenyliodonium triflate,
0.1 mmol anhydrous CuI, 0.5 mmol Cs2CO3, 5 ml diox-
ane. The test tube was sealed with a sleeve rubber stopper
FIGURE 1 Some reactions related to tosylhydrazones
FIGURE 2 Representative bioactive
indazoles and sulfonamide derivatives

WU ET AL.
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and evacuated and refilled with argon for three cycles.
The mixture was stirred under room temperature for
24 hrs. And then the reaction mixture was quenched with
water, added with 2 ml saturated NaCl solution, and
extracted with ethyl acetate (20 ml) for three times. The
combined organic layer was dried with anhydrous
MgSO4, and condensed in vacuum on a rotary evaporator.
The residual was purified on a silica gel chromatograph
column by means of gradient elution (eluent: petroleum
ether/ethyl acetate) to give the desired product.
First of all, diphenyliodonium triflate and L‐
phenylalaninamide were adopted as the model substrates
(Table 1). Given that several catalyst‐free C‐N coupling
reactions with diaryliodonium salts were reported, the
two reactants were performed at room temperature under
the catalyst‐free condition, but only trace product was
detected on TLC (entry 1). When Pd (OAc)2 was used as
catalyst for this reaction, the yield was very low (Entry 2).
To investigate suitable reaction temperatures, a series
of temperatures were screened including RT, 40°C, 60°C,
90°C. When temperature was lower than 60°C, the higher
temperature, the higher yield. But while the temperature
was higher than 60°C, the yield did not improve as
expected (entries 20–22 vs. 5). It seemed that high tem-
perature causes tosylhydrazones to decompose. Shorten-
ing the reaction time resulted in lower yields (entries
23–25), but too long time was unnecessary (entry 26).
3 | RESULTS AND DISCUSSION
During the primary experimentation, many reaction con-
ditions were screened. Finally, in the presence of CuI and
Cs2CO3, the reaction afforded a product, which was veri-
fied to be the C‐N coupling product N′‐benzylidene‐4‐
Under
the
optimized
reaction
conditions,
methyl‐N‐phenylbenzenesul‐fonohydrazide.
Therefore
tosylhydrazones with various substituents were evaluated
to react with diphenyliodonium triflate (Table 2). Particu-
larly, tosylhydrazones with all kinds of substituents could
react with diphenyliodonium triflate (entries 1–14).
Reaction of benzaldehyde tosylhydrazones and
diaryliodonium triflate gave product 3a with 94% yield
(entry 1). The structure of 3a was further confirmed by
single‐crystal X‐ray structure analysis (Figure 3).
Tosylhydrazones both with electron‐rich and ‐deficient
functional groups at the para‐position of the aryl ring
afforded the desired products in good yields (entries
2–8). In addition, when acetophenone tosylhydrazones
was employed as the substrate, the corresponding product
3i was obtained with a high yield (entry 9). 2,2,2‐
Trifluoro‐1‐phenylethan‐1‐one tosylhydrazones was also
a suitable substrate, the desired coupling product 3j was
obtained in 88% yield (entry 10).
Cinnamaldehyde is an essential skeleton of many
biologically active organic compounds that have found
wide applications in pesticides and medicines. To further
investigate the potential range of the coupling reaction,
tosylhydrazone with cinnamaldehyde block was
researched as a substrate, giving a 68% 3 k. It is worth
mentioning that the product 3 l was also obtained from
the coupling reaction of naphthaldehyde tosylhydrazone
and diaryliodonium triflate. 2‐Chlorobenzaldehyde and
3,4‐dichlorobenzaldehyde tosylhydrazones could also be
used as substrates to afford the corresponding products
3 m and 3n in 83% and 88% yields, respectively.
we found a C‐N coupling protocol for the highly reactive
tosylhydrazones, and we investigated the C‐N coupling
reaction in detail in the following (Scheme 1).
Benzaldehyde
tosylhydrazones
1a
and
diphenyliodonium triflate 2a were selected as the model
substrates to establish an optimized reaction condition,
and the selected results were listed in Table 1.
Initially, since there were several catalyst‐free C–N
coupling reactions reported, the reaction was performed
at 60°C under the catalyst‐free condition, but only trace
of the product was detected on TLC (entry 1). While Pd
(OAc)2 was used as a catalyst for this reaction, no product
3a was obtained (entry 2). Next, given that the C‐N cou-
pling reactions in the presence of I2 had been
reported,[52,53] I2 was used as catalyst, but the reaction
gave no desired product 3a (entry 3). Therefore, various
copper salts, such as CuBr, CuCl, CuI, Cu (OAc)2, and
CuCl2, were used in the C‐N coupling reaction. The
different cuprous and cupric salts had significantly effect
on the yield of product 3a (entries 4–8). When cupric salts
was took part in the coupling reaction, the yield of
product 3a increased greatly. The yields of the coupling
reactions with Cu (OAc)2 and CuCl2 as catalyst are 88%
and 71%, respectively (entries 7–8). Compared with the
catalyst cupric salts, cuprous salts offered much higher
yields. Both CuBr and CuCl obtained higher yields of
86% and 80% (entries 4 and 6). Surprisingly, CuI exhibited
an excellent catalytic result with the highest yield of 94%
(entry 5).
SCHEME 1 Copper‐catalyzed C‐N
coupling reaction of tosylhydrazones 1
and diaryliodonium salts 2

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WU ET AL.
TABLE 1 Optimization of the reaction conditions of benzaldehyde tosylhydrazones 1a and diaryliodonium triflate 2aa
Entry
Base
Catalyst
Solvent
T(°C)
Yield[%]
1
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Na2CO3
K2CO3
KOH
‐‐‐
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
DMSO
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
RT
40
90
60
60
60
60
Trace
Trace
Trace
80
2
Pd (OAc)2
I2
3
4
CuCl
CuI
5
94
6
CuBr
Cu (OAc)2
CuCl2
CuI
86
7
88
8
71
9
20
10
11
12
13
14
15
16
17
18
19
20
21
22
23b
24c
25d
26e
CuI
DMF
33
CuI
Methanol
THF
76
CuI
71
CuI
Toluene
64
CuI
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
1,4‐dioxane
73
CuI
68
CuI
54
NaOH
CuI
60
K3PO4
CuI
88
NaOtBu
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
CuI
30
CuI
Trace
28
CuI
CuI
92
CuI
26
CuI
62
CuI
80
CuI
91
aReaction conditions: tosylhydrazones (0.5 mmol), diphenyliodonium triflate (0.7 mmol), catalyst (0.1 mmol), base (0.5 mmol) in 5 ml of solvent for 24 h in
argon. Reaction were performed at 60 °C, unless otherwise noted. Reaction time:
b6 h,
c12 h,
d18 h,
e30 h. Yields correspond to isolated products.
Subsequently, to investigate the scope of
diaryliodonium salts, various diaryliodonium salts were
examined to react with benzaldehyde tosylhydrazones
(Table 3). First of all, diphenyliodonium salts with
various equilibrium anions were investigated (entries 1
to 6). It is reported that the solubility and reactivity of
the diaryliodonium salts was heavily affected by the
equilibrium anion (X−).[54] However, for our coupling
reaction, the effect of equilibrium anions is not obvious.
Diphenyliodonium hexafluorophosphate gave a yield of
86% (entry 2), and diphenyliodonium nitrate (entry 2)
and halide anions (entries 3–5) gave slightly lower yields
in a range of 74% and 82%. And diphenyliodonium triflate
corresponds to 94% yield of the product (entry 1), so

WU ET AL.
5 of 8
TABLE 2 The reaction of tosylhydrazones with various substituents 1 and diphenyliodonium triflate 2aa
Entry
R1
R2
Product
Yield[%]
1
C6H5
H
3a
94
73
90
85
80
85
70
85
92
88
68
71
83
88
2
4‐NO3C6H4
4‐ClC6H4
H
3b
3c
3
H
4
4‐BrC6H4
4‐CNC6H4
4‐CH3C6H4
4‐CH3OC6H4
4‐(CH3)2NC6H4
C6H5
H
3d
3e
5
H
6
H
3f
7
H
3 g
3 h
3i
8
H
9
Me
CF3
H
10
11
12
13
14
C6H5
3j
C6H5CH=CH
1‐Naphthyl
2‐ClC6H4
3 k
3 l
3 m
3n
Me
H
3,4‐(Cl)2C6H4
H
aReaction condition: tosylhydrazones (0.5 mmol), diaryliodonium triflate salt (0.7 mmol), CuI (0.1 mmol), Cs2CO3 (0.5 mmol) in 5 ml of 1, 4‐dioxane for 24 h in
argon at 60 °C. Yields correspond to isolated products.
FIGURE 3 Single crystal X‐ray structure of 3a

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WU ET AL.
a
TABLE 3 The reaction of benzaldehyde tosylhydrazones 1a and a variety of diaryliodonium salt 2
Entry
Ar
Xˉ
Product
Yield[%]
1
C6H5
OTfˉ
PF6ˉ
NO3ˉ
Clˉ
3a
3a
3a
3a
3a
3a
3o
3p
3q
3r
94
86
82
80
74
77
83
85
68
93
88
74
78
98
2
C6H5
3
C6H5
4
C6H5
5
C6H5
Brˉ
6
C6H5
Iˉ
7
4‐CH3C6H4
4‐t‐C4H9C6H4
3,4‐(CH3)2C6H3
2,4‐(CH3)2C6H3
2,5‐(CH3)2C6H3
2‐CH3–5‐t‐C4H9C6H3
2‐CH3–5‐BrC6H3
Diphenyleneiodonium (Ar2I+)
OTfˉ
OTfˉ
OTfˉ
OTfˉ
OTfˉ
OTfˉ
OTfˉ
OTfˉ
8
9
10
11
12
13
14
3 s
3 t
3u
3v
aReaction conditions: benzaldehyde tosylhydrazones (0.5 mmol), diaryliodonium salt (0.7 mmol), CuI (0.1 mmol), Cs2CO3 (0.5 mmol) in 5 ml of 1, 4‐dioxane for
24 hr in argon. Reaction were performed at 60 °C. Yields of the isolated products are given.
triflate was the best equilibrium anion for the C–N
coupling reaction.
At the beginning of this study, we use classical and
cheaper iodobenzene to carry out the C‐N coupling reac-
tion instead of diaryliodonium salts. However, experi-
ments showed that the reaction of benzaldehyde
tosylhydrazones 1a and iodobenzene couldn't give the
product 3a under the same condition. We think that the
reason is the lower activity of iodobenzene than
diaryliodonium salts. The product 3v (entry 14) with the
structure of iodobenzene confirms the speculation
(Scheme 2).
Based on the above experimental results, a plausible
mechanism of copper‐catalyzed C‐N coupling reaction
of diphenyliodonium salts and tosylhydrazones is pro-
posed (Scheme 3). First, copper (I) salt (CuX, X = I, Br,
Cl, etc.) and the tosylhydrazone 1 forms a complex 4.
Under the basic condition, the proton and the X of com-
plex 4 is removed by Cs2CO3. Then an active complex 5
with two empty coordination sites is formed. The Cu (I)
Diaryliodonium triflates of para‐substituted alkyl
groups gave the products in high yields (entries 7–8). Di
(3,4‐dimethylphenyl) iodonium triflate afforded the corre-
sponding C–N coupling products in yield of 68% (entries
9). All of the bulky ortho‐substituted di (2,4‐dimethylph‐
enyl) iodonium triflate, di (2,5‐dimethylphenyl) iodonium
triflate and di (2‐methyl‐5‐tert‐butylphenyl) iodonium
triflate afforded pretty high yields (entry 10–13), as sug-
gests that the steric hindrance of diaryliodonium triflates
has little or no effect on the reaction. Di (2‐methyl‐5‐
bromo) iodonium triflate with electron‐poor aryl group
gave the corresponding product with a similar yield to that
of diaryliodonium triflates with electron‐rich groups
(entry 13 vs. 7–12).
In surprise, diphenyleneiodonium triflate which has an
amazing iodo‐containing five‐membered ring structure
can perform a similar reaction and offered a product 3v
with an extremely high yield of 98% (entry 14).
complex
5 undergoes oxidative addition with the
diphenyliodonium salt. And a Cu (III) complex 6 is
SCHEME 2 The reaction of
benzaldehyde tosylhydrazones 1a and
diphenyleneiodonium triflate 2v

WU ET AL.
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ACKNOWLEDGMENTS
We thank the Department of Science and Technology of
Sichuan Province (No. 2016HH0074), Chengdu Science
and Technology Bureau (No. 2015‐HM01‐00362‐SF) and
the State Key Laboratory of Geohazard Prevention and
Geoenvironment Protection Independent Research Project
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ORCID
Qingle Zeng http://orcid.org/0000-0003-0750-540X
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