Palladium-catalyzed direct ortho-sulfonylation of azobenzenes with arylsulfonyl chlorides via C-H activation

Article abstract of DOI:10.1039/c5ra06474k

A highly efficient and practical procedure to direct ortho-sulfonylation of azobenzenes' C-H bond with arylsulfonyl chlorides has been developed. The method was applicable to both electron-rich and electron-deficient substrates and delivered good yields f

Full text of DOI:10.1039/c5ra06474k

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Palladium-catalyzed direct ortho-sulfonylation of azobenzenes with
arylsulfonyl chlorides via C-H activation
a, c
c
b
b
a
a
Chengcai Xia, Zhenjiang Wei, Chao Shen, Jun Xu, Yong Yang, Weike Su *
b,a
and Pengfei Zhang
*
a
Pharmacy College, Zhejiang University of Technology, Hangzhou 310014, China
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal
b
University, Hangzhou 310036 China
c
Pharmacy College, Taishan Medical University, Tai’an 271016, China
Fax: +86-571-28862867; Tel: +86-571-28862867;
E-mail: chxyzpf@hotmail.com
Ortho-sulfonylated azobenzenes were obtained in moderate to high yields by direct
ortho-sulfonylation of azobenzenes C-H bond with arylsulfonyl chlorides.

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ARTICLE TYPE
Palladium-catalyzed direct ortho-sulfonylation of azobenzenes with
arylsulfonyl chlorides via C–H activation
a, c
c
b
b
a
a
b,a
Chengcai Xia, Zhenjiang Wei, Chao Shen, Jun Xu, Yong Yang, Weike Su * and Pengfei Zhang
*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
A highly efficient and practical procedure to direct orthoꢀsulfonylation of azobenzenes CꢀH bond with arylsulfonyl chlorides has been
developed. The method was available for both electronꢀrich and electronꢀdeficient substrates which have good yields for 21 examples.
This reaction provides a convenient access to orthoꢀsulfonylated azobenzenes under mild conditions.
‡
Footnotes should appear here. These might include comments relevant
1
0
Introduction
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
Transitionꢀmetalꢀcatalyzed CꢀC and C–heteroatom bonds
formation via CꢀH bond activation have been broadly explored
because it is an efficient method to construct heterocyclic
5
5
6
6
7
0
5
0
5
0
Aryl sulfones have attracted considerable interests for their are
essential components in medicinal chemistry , synthetic
intermediate and advanced organic materials. The increasing
applications of sulfones have stimulated investigations on
development of efficient processes for the synthesis of these
compounds. For example, Xu reported
palladiumꢀcatalyzed direct sulfonylation of 2ꢀaryloxypyridines on
the orthoꢀposition of the benzene ring using 2ꢀpyridyloxyl as the
directing group and sulfonyl chlorides as sulfonylation reagents.
Saidi has developed an efficient meta sulfonation of
17
1
compounds. Recently, more and more effort has been made to
18
19
1
2
2
3
3
5
0
5
0
5
develop many techniques to control the reaction selectivity
assistance of
a directing group. Among them, such as
2
3
4
2
ꢀaryloxypyridines , quinoline NꢀOxide , arylpyrazoles , triazene
5
6
7
a
method of
azoxybenzenes , quinoline , and 2ꢀarylꢀ1,2,3ꢀtriazoles group , etc.
were proved to be a versatile directing group to obtain the high
2
regioselectivity on the orthoꢀC(sp )ꢀH bond. In recent years, the
azobenzenes work as directing group to accelerate the CꢀH
activation/functionalization process have attracted more
attentions. For example, many groups have developed
palladiumꢀcatalyzed regioselective CꢀH bond activation of
2
0
2
1
2
ꢀphenylpyridines in the presence of ruthenium(II) complexes.
a
Zhao disclosed
sulfonylation of 2ꢀarylpyridines on the orthoꢀposition of the
benzene ring using 2ꢀarylpyridine as the directing group. Wu’s
group reported Pd(II)ꢀcatalyzed CꢀH sulfonylation of
azobenzenes with arylsulfonyl chlorides using K S O as
a
method of palladiumꢀcatalyzed direct
8
9
azoarenes and related compounds with a alcohols , toluene ,
2
2
10
11
aldehydes , and aꢀoxocarboxylic acids
to synthesis
orthoꢀacylazoarenes. But, Sun and coꢀworkers find they get
orthoꢀalkoxyazoarenes when PhI(OAc) has been added as the
2
2
8
2
23
1
2
oxidant.
oxidant in this reaction. Also, Hao and Li’s group have
developed a highly efficient method to synthesis of diverse
cinnolines and isoquinolines through the rhodiumꢀcatalyzed
oxidative CꢀH activation of azobenzenes and ketazines with
As a part of our continuing efforts in CꢀH bond activation
reaction, we have recently developed many methods to formation
CꢀS, CꢀC bonds. Based on these findings, we develop a simple
and efficient procedure for the synthesis of various
orthoꢀsulfonylated azobenzenes via palladiumꢀcatalyzed direct
crossꢀcoupling of azobenzenes with arylsulfonyl chlorides.
24
13
alkynes.
Similarly, azobenzenes derivatives such as orthoꢀ
1
4
15
acyloxyazoarenes , orthoꢀSulfonamideazoarenes , and orthoꢀ
1
6
arylazoarenes have been synthesized by this method.
a
Pharmacy College, Zhejiang University of Technology, Hangzhou
10014, China
College of Material, Chemistry and Chemical Engineering, Hangzhou
75 Results and discussion
3
We initiated our investigation on the model reaction of
b
azobenzene (1a) with pꢀtolylsulfonyl chloride (2a) to optimize
the reaction parameters (Table1). To our delight, the C2ꢀ
4
4
0
5
Normal University, Hangzhou 310036 China
c
Pharmacy College, Taishan Medical University, Tai’an 271016, China
Fax: +86-571-28862867; Tel: +86-571-28862867;
E-mail: chxyzpf@hotmail.com
sulfonylation took place in the presence of Pd(OAc) (10 mol%)
and K CO (2 equiv) in DMSO under air for 12 h, affording
2 3
compound 3a in 41% yield (entry 1, Table1). Without catalyst,
the reaction could not take place at all. Thus, PdCl2,
2
80
1
†
Electronic Supplementary Information (ESI) available:
H NMR
1
3
spectra,
C NMR spectrum, GC/MS profile, HRMS profile. See
DOI: 10.1039/b000000x/
[
PdCl(allyl)] , Pd(COD)Cl , Pd(CH CN) Cl , CuI and CuCl were
2 2 3 2 2
tested to catalyze this reaction, in which Pd(CH CN) Cl gave the
3
2
2
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best result (entries 1ꢀ7, Table1). K CO was superior to other
yields(67%, 63%). Heteroarysulfonyl chlorides, such as 3,5ꢀ
dimethylꢀisoxazoleꢀ4ꢀsulfonyl chloride, thiopheneꢀ2ꢀsulfonyl
2
3
bases, such as Na CO , KOAc, NaOAc, CsCO , NaHCO and KF
2
3
3
3
(entries 8ꢀ13, Table1). The solvent also played an important role
chloride,
5ꢀchloroꢀ3ꢀmethylbenzo[b]thiopheneꢀ2ꢀsulfonyl
in the reaction. Solvents such as DMF, NMP, CH CN, 40 chloride, and methyl 2ꢀ(chlorosulfonyl)thiopheneꢀ3ꢀcarboxylate
3
5
1,4ꢀdioxane, toluene, and DMSO were screened, and 1,4ꢀdioxane
was found to be superior to the others (entries 5 and 14ꢀ18),
affording 3a in 92% yield (entry 17, Table1). The yield decreased
to 73% when the catalyst loading was reduced to 5mol % from 10
mol % (entry 19, Table1). After surveying a variety of catalysts,
bases, solvents, and catalyst loadings, we found that the
combination of 10 mol % of Pd(CH CN) Cl and 2 equiv of
were tested as the substrates. The corresponding orthoꢀ
sulfonylation products 3h, 3i, 3j, and 3k were obtained in good
yields (73ꢀ90%).
a
Table 2. Preparation of Sulfones from Various Sulfinates
1
0
3
2
2
K CO in 1,4ꢀdioxane at 130 °C for 12 h served as the optimal
45
2
3
b
Entry
1
Sulfinates
Product
Yield( %)
92
conditions for this transformation. These results indicated that
this transformationwas facile and practical, as it did not require
the use of strong bases, and the oxidants exclusion of air.
1
5
a
Table 1. Optimization of Reaction Conditions.
2
3
4
7
6
b
Entry
Catalyst
Base
Solvent
DMSO
Yield(%)
41
1
2
3
4
5
6
7
8
9
Pd(OAc)
2
K
2
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
86
PdCl
[PdCl(allyl)]
Pd(COD)Cl
2
K
2
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
33
39
2
K
2
2
K
2
15
6
7
7
Pd(CH
3
CN)
2
Cl
2
K
2
77
CuI
K
2
N.R.
N.R.
40
CuCl
K
2
5
Pd(CH
3
3
3
3
3
CN)
2
2
2
2
2
Cl
Cl
Cl
2
2
2
2
2
Na
KOAc
NaOAc
Cs CO
2
CO
3
5
Pd(CH
Pd(CH
CN)
CN)
31
1
0
35
1
1
1
1
1
1
2
3
4
5
Pd(CH
Pd(CH
Pd(CH
Pd(CH
Pd(CH
CN)
CN)
CN)
CN)
CN)
Cl
Cl
Cl
Cl
Cl
2
3
DMSO
DMSO
DMSO
DMF
44
23
31
45
67
O
S
6
7
8
O
O2N
NaHCO
3
Cl
63
3
3
3
2
2
2
2
2
2
KF
K
2
CO
CO
CO
3
K
2
3
NMP
8
9
4
0
1
1
1
1
6
7
8
9
Pd(CH
3
CN)
2
Cl
2
K
2
3
CH
3
CN
73
92
21
Pd(CH
3
CN)
2
Cl
2
K
2
CO
3
dioxane
toluene
dioxan
Pd(CH
Pd(CH
3
CN)
CN)
2
Cl
2
2
K
2
CO
CO
3
c
3
2
Cl
K
2
3
73
a
Reaction conditions:1a (0.5 mmol), 2a (0.6 equiv), catalyst (10 mol %),
base (2.0 equiv), 4A MS (100 mg) and solvent (2.0 mL) under air at
b
c
2
0
130 °C for 12 h, unless otherwise noted. Isolated yields.
Pd(CH CN) Cl (5 mol %).
9
3
2
2
N
N
O
8
8
7
9
With the optimized reaction conditions in hand, the reactivities of
different arylsulfonyl chlorides as the sulfonylation reagents were
investigated. The results are revealed in Table 2, the CꢀH
sulfonylation of azobenzene (1a) with arylsulfonyl chlorides
could proceed smoothly and furnish the corresponding
orthoꢀsubstituted products 3a-n in 63ꢀ92% yields (Table2, entries
S
O
i
S
3
2
5
10
11
1
ꢀ14). The substrates with a paraꢀelectronꢀdonating group
3
0
afforded the products 3a , 3g , 3n in excellent yields (92% , 84%
and 91%). When arylsulfonyl chlorides were substituted at the
para position with a electronꢀwithdrawing group (such as 4ꢀF,
73
4
ꢀBr, 4ꢀmethoxy, 4ꢀCl groups) there also afforded the products
3
b, 3c, 3d and 3m in good yields (75ꢀ86%). But the substrates
3
5
with a strong electronꢀwithdrawing group (ꢀNO ) on para and
2
meta position provided the corresponding product 3d , 3f in low
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1
1
2
3
90
corresponding products in 75ꢀ86% yields (3o-3r). The reactions
2
0
of unsymmetrical azobenzenes also proceeded smoothly and gave
1
the products which could be determined by H NMR, were
obtained in good yields (71% for 3t; 78% for 3u, respectively).
A single crystal of 3b was obtained from trichloromethane. Its
crystal structure (Fig. 1) exhibited that such palladiumꢀcatalyzed
direct sulfonylation of azobenzene on the orthoꢀposition. The
crystal data, refinement parameters, bond lengths and bond angles
are given in the Table S1.
82
91
25
1
4
a
30
Reaction conditions:1a (0.5 mmol), 2 (0.6 equiv), catalyst (10 mol %),
base (2.0 equiv), 4A MS (100 mg) and solvent (2.0 mL) under air at
b
1
30 °C for 12 h, unless otherwise noted. Isolated yields.
a
5
Table 3. Preparation of Sulfones from Various azoarenes
35
b
Entry
1
Azoarenes
Product
Yield( %)
40
Fig 1 ORTEP diagram of catalyst 3b showing atomlabelling scheme.
Hydrogen atoms are omitted for clarity. Thermal ellipsoids are drawn at
30% probability.
N
N
O
S
8
7
6
5
O
3
o
2
3
8
8
3
5
4
5
6
45
Scheme 1. Plausible Reaction Mechanism
In addition, when some radical scavengers such as TEMPO
15
71
(2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy) or HQ (Hydroquinone)
5
5
6
0
5
0
were used in this CꢀS coupling reaction, the reaction can be
carried out smoothly. So this experiment can exclude the free
radical mechanism. On the basis of thses results and other
N
N
O
O
N
N
O
S
O
19ꢀ22
previous related studies,
a plausible reaction mechanism of
3t
this palladiumꢀcatalyzed sulfonylation of an azobenzene
compounds is proposed, as shown in Scheme 1. Step (i) ,
azobenzene 1a firstly reacts with Pd(CH CN) Cl to form a
7
81
3
2
2
cyclopalladated (II) intermediate through orthoꢀCꢀH bond
insertion. In step (ii), the sulfonylation could go through a direct
displacementꢀtype reaction to give the final product 3a.
Meanwhile, the Pd(II) was regenerated for the next catalytic
cycle.
a
Reaction conditions:1a (0.5 mmol), 2 (0.6 equiv), catalyst (10 mol %),
base (2.0 equiv), 4A MS (100 mg) and solvent (2.0 mL) under air at
b
1
30 °C for 12 h, unless otherwise noted. Isolated yields.
1
0
After screening of different arylsulfonyl chlorides, we explored
the scope of differently substituted azobenzenes. Representative
azoxybenzenes were firstly synthesized and examined. The
results are shown in table 3. It was found that these electronꢀrich
azobenzenes gave higher yields than those electronꢀdeficient
azobenzenes. For instance, the reactions of 4,4’ꢀdimethylꢀ
azoxybenzene, 3,3’ꢀdimethylazoxybenzene, 4,4’ꢀdi methoxy
azoxybenzene, 3,3’ꢀdi methoxy azoxybenzene, provided the
Conclusions
In conclusion, we have developed a palladiumꢀcatalyzed direct
2
65
C(sp )ꢀH sulfonylation of azobenzene with arylsulfonyl Chlorides.
The reaction exhibits a good tolerance for a broad range of
general functional groups. The present work demonstrated the
utility of azobenzene as a removable directing group through the
1
5
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+
direct CꢀH bond activation/functionalization and deprotecting
14.80.HRMS (ESI+): Calculated for C H N O : [M+H]
16 18 2 2
group to form orthoꢀsulfonylated azobenzenes.
60 270.1368, Found 271.1373.
Experimental section
(E)-1,2-bis(3-methoxyphenyl)diazene.
o
1
5
General information
Obtained as a yellow solid in 85% yield; M.p. 70ꢀ71 C. H NMR
(500 MHz, CDCl ) δ 7.49 (ddd, J = 7.8, 1.6, 0.9 Hz, 2H), 7.40 –
All reactions were run under argon in Schlenk tubes using
3
vacuum lines. DMF, NMP, CH CN, 1,4ꢀdioxane, toluene, and 65 7.37 (m, 2H), 7.36 (t, J = 8.0 Hz, 2H), 6.98 (ddd, J = 8.2, 2.6, 0.8
3
1
3
DMSO, analytical grade were not distilled before use.
Commercial arylsulfonyl chlorides and azobenzenes were used
Hz, 2H), 3.83 (s, 6H). C NMR (126 MHz, CDCl
) δ 159.31,
3
152.79, 128.76, 116.85, 116.14, 104.69, 54.46. HRMS (ESI+):
Calculated for C14H N O : [M+H] 243.1128, Found 243.0686.
14 2 2
1
13
+
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
without purification. H NMR, C NMR spectra were recorded
using a 500 MHz spectrometer in CDCl and DMSO with shifts
3
referenced to SiMe (δ = 0). IR spectra were recorded on an FTIR 70 (E)-1-(3-methoxyphenyl)-2-phenyldiazene.
4
o
1
spectrophotometer. Melting points were determined by using a
local hotꢀstage melting point apparatus and are uncorrected.
Elemental analyses were carried out on a CHN analyzer. Mass
spectra were recorded using LCꢀMS and HRMS (ESIꢀTOF
analyzer) equipment.
Obtained as a yellow solid in 60% yield; M.p.30ꢀ31 C. H NMR
(500 MHz, CDCl ) δ 7.95 – 7.89 (m, 2H), 7.57 – 7.41 (m, 6H),
7.07 – 7.02 (m, 1H), 3.90 (s, 3H). C NMR (126 MHz, CDCl
160.34, 153.91, 152.61, 131.05, 129.80, 129.11, 122.89, 117.83,
3
13
) δ
3
75 117.14, 105.74, 55.50. HRMS (ESI+): Calculated for C13
H
N
2
O
1
:
12
+
General procedure for preparation of azoxybenzenes
All of the azoꢀcompounds were prepared from arylamines,
[M+H] 213.1022, Found 213.061.
[
1]
according to the literature. Mix CuBr (4.2 mg, 0.03 mmol),
pyridine (8.7 mg, 0.09 mmol), arylamines (93 mg, 1 mmol) in
(E)-1-(3-methoxyphenyl)-2-(m-tolyl)diazene.
1
Obtained as a yellow liquid in 58% yield. H NMR (500 MHz,
toluene (4 ml) under air (1 atm). The reaction mixture was 80 CDCl ) δ 7.73 (d, J = 5.8 Hz, 2H), 7.55 (ddd, J = 7.8, 1.5, 1.0 Hz,
3
vigorously stirred at 60 °C for 20 h. After cooling down to room
temperature and concentrating in vacuum, the residue was
purified by flash chromatography on a short silica gel (eluent:
petroleum ether) to afford azoꢀcompound.
General procedure for Palladium-Catalyzed Direct 85 117.72, 117.04, 105.69, 55.47, 21.37. HRMS (ESI+): Calculated
ortho-Sulfonylation of Azobenzenes with Arylsulfonyl
Chlorides via C-H Activation
1H), 7.46 – 7.44 (m, 1H), 7.41 (dd, J = 16.4, 8.3 Hz, 2H), 7.29 (d,
J = 7.5 Hz, 1H), 7.03 (ddd, J = 8.2, 2.6, 0.8 Hz, 1H), 3.89 (s, 3H),
2.45 (s, 3H), 2.45 (s, 1H). C NMR (126 MHz, CDCl
13
) δ 160.32,
3
153.94, 152.68, 138.99, 131.83, 129.76, 128.91, 122.93, 120.55,
+
for C14H N O : [M+H] 227.1179, Found 227.075.
14 2 1
Mix azoic compound (0.5equiv), benzene sulfonyl chloride
(E)-1-phenyl-2-(2-tosylphenyl)diazene. (3a)
Obtained as a white solid in 78% yield; M.p. 157ꢀ158 C. H
NMR (500 MHz, CDCl ) δ 8.40 (dd, J = 7.7, 1.5 Hz, 1H), 7.86 –
.80 (m, 4H), 7.65 (dtd, J = 22.0, 7.5, 1.4 Hz, 2H), 7.58 (dd, J =
.7, 1.3 Hz, 1H), 7.55 – 7.50 (m, 3H), 7.16 (d, J = 8.2 Hz, 2H),
.32 (s, 3H). C NMR (126 MHz, CDCl ) δ 152.72, 149.07,
43.91, 139.43, 138.88, 134.35, 131.97, 130.54, 129.35, 129.29,
129.11, 128.20, 123.77, 116.90, 21.51. HRMS (ESI+): Calculated
for C H N O S: [M+H]+ 336.0916, Found 337.0989.
o
1
(0.6equiv), Pd(CH CN) Cl (10 mol%), K CO (2 equiv), 4A MS
3 2 2 2 3
9
0
(100 mg) in 1,4ꢀdioxane (2 ml) under air. The reaction mixture
3
7
7
2
1
was vigorously stirred at 130 °C for 12 h. After cooling down to
room temperature and concentrating in vacuum, the residue was
purified by flash chromatography on a short silica gel to afford
corresponding product.
13
3
95
23
18
2
3
1
Diazene. (1a)
(
E)-1,2-di-p-tolyldiazene.
(E)-1-(2-((4-bromophenyl)sulfonyl)phenyl)-2-phenyldiazene.
o
1
Obtained as a yellow solid in 90% yield; M.p. 138ꢀ140 C. H
(3b)
o
1
NMR ( 500 MHz, CDCl ) δ 7.81 (d, J = 8.3 Hz, 4H), 7.30 (d, J = 100 Obtained as a orange solid in 66% yield; M.p. 200ꢀ201 C. H
3
1
3
8
.0 Hz, 4H), 2.42 (s, 6H). C NMR (126 MHz, CDCl ) δ 150.85,
NMR (500 MHz, CDCl ) δ 8.39 (d, J = 7.8 Hz, 1H), 7.84 – 7.78
(m, 4H), 7.71 (t, J = 7.6 Hz, 1H), 7.65 (t, J = 7.5 Hz, 1H), 7.60 (d,
J = 7.8 Hz, 1H), 7.56 – 7.52 (m, 3H), 7.52 – 7.48 (m, 2H).
NMR (126 MHz, CDCl ) δ 152.68, 148.96, 141.34, 138.17,
3
3
1
41.22, 129.73, 122.75, 21.50. HRMS (ESI+): Calculated for
+
13
C H N : [M+H] 211.123, Found 211.1032.
C
1
4
14
2
3
(
E)-1,2-di-m-tolyldiazene
105 134.82, 132.20, 131.96, 130.71, 129.78, 129.42, 129.23, 128.20,
123.67, 117.06. HRMS (ESI+): Calculated for C H BrN O S:
o
1
Obtained as a yellow solid in 87% yield; M.p. 123ꢀ124 C. H
18
13
2
2
+
NMR (500 MHz, CDCl ) δ 7.71 (s, 4H), 7.40 – 7.34 (m, 2H),
[M+Na] 422.9773, Found 422.9178.
3
1
3
7
.25 (d, J = 7.0 Hz, 2H), 2.42 (d, J = 3.0 Hz, 6H). C NMR (126
MHz, CDCl ) δ 152.87, 139.00, 131.75, 128.95, 122.97, 120.54,
(E)-1-(2-((4-fluorophenyl)sulfonyl)phenyl)-2-phenyldiazene.
3
+
2
1.43. HRMS (ESI+): Calculated for C H N : [M+H] 211.123, 110 (3c)
1
4
14
2
o
Found 211.1034.
Obtained as a orange solid in 86% yield; M.p. 107ꢀ108 C.
H NMR (500 MHz, CDCl ) δ 8.40 (dd, J = 7.8, 1.4 Hz, 1H),
8.00 – 7.95 (m, 2H), 7.83 – 7.79 (m, 2H), 7.70 (dd, J = 7.7, 1.5
Hz, 1H), 7.65 (td, J = 7.6, 1.4 Hz, 1H), 7.60 (dd, J = 7.8, 1.3 Hz,
1
3
(
E)-1,2-bis(4-ethoxyphenyl)diazene.
o
1
Obtained as a yellow solid in 92% yield; M.p. 150ꢀ151 C. H
13
NMR (500 MHz, CDCl ) δ 7.91 – 7.82 (m, 4H), 6.98 (d, J = 8.9 115 1H), 7.57 – 7.53 (m, 3H), 7.03 (t, J = 8.6 Hz, 2H). C NMR (126
3
13
Hz, 4H), 4.10 (q, J = 7.0 Hz, 4H), 1.44 (t, J = 7.0 Hz, 6H). C
MHz, CDCl ) δ 152.69, 148.95, 138.43, 134.70, 132.16, 131.12,
3
NMR (126 MHz, CDCl ) δ 161.01, 146.93, 124.36, 114.66, 63.79,
131.05, 130.67, 129.35, 129.21, 123.66, 117.04, 116.01, 115.83.
3
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DOI: 10.1039/C5RA06474K
+
HRMS (ESI+): Calculated for C H FN O S: [M+Na] 341.0755,
Calculated for C H N O S: [M+H]+ 342.0907, Found
17 15 3 3
1
8
13
2
2
Found 341.0211.
342.0377.
60
(
E)-1-(2-((4-nitrophenyl)sulfonyl)phenyl)-2-phenyldiazene.
(E)-1-phenyl-2-(2-(thiophen-2-ylsulfonyl)phenyl)diazene. (3i)
Obtained as a white solid in 87% yield; M.p. 100ꢀ101 C. H
o
1
5
0
5
0
5
0
5
0
5
0
5
(3d)
o
Obtained as a pale yellow solid in 67% yield; M.p. 134ꢀ135 C.
NMR (500 MHz, CDCl ) δ 8.37 (d, J = 8.0 Hz, 1H), 8.06 – 7.98
3
1
H NMR (500 MHz, CDCl ) δ 8.44 (d, J = 7.8 Hz, 1H), 8.19 (d, J
(m, 2H), 7.82 – 7.77 (m, 1H), 7.76 – 7.69 (m, 2H), 7.68 – 7.63 (m,
3
13
=
4
8.2 Hz, 2H), 8.13 (d, J = 8.5 Hz, 2H), 7.74 (qd, J = 15.1, 7.5 Hz, 65 1H), 7.63 – 7.53 (m, 4H), 7.00 (t, J = 4.4 Hz, 1H). C NMR (126
13
H), 7.65 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 5.8 Hz, 3H). C NMR
MHz, CDCl ) δ 152.67, 149.00, 143.44, 139.35, 134.53, 134.38,
3
1
1
2
2
3
3
4
4
5
5
(126 MHz, CDCl ) δ 152.57, 150.15, 148.90, 148.06, 137.29,
134.06, 132.12, 130.82, 129.25, 129.21, 127.23, 124.09, 116.89.
HRMS (ESI+): Calculated for C H N O S : [M+H]+ 329.0413,
Found 329.0336.
3
1
35.42, 132.50, 130.92, 129.65, 129.36, 123.90, 123.57, 117.21.
16
12
2
2 2
+
HRMS (ESI+): Calculated for C H N O S: [M+H] 368.07,
1
8
13
3
4
Found 368.0128.
70
(
E)-1-(2-((5-chloro-3-methylbenzo[b]thiophen-2-yl)sulfonyl)p
(E)-1-(2-((4-methoxyphenyl)sulfonyl)phenyl)-2-phenyldiazene.
3e)
Obtained as a white solid in 75% yield; M.p. 139ꢀ140 C. H
henyl)-2-phenyldiazene. (3j)
o
(
Obtained as a pale yellow solid in 89% yield; M.p. 156ꢀ157 C.
o
1
1
H NMR (500 MHz, CDCl ) δ 8.45 (d, J = 7.7 Hz, 1H), 7.87 (d, J
3
NMR (500 MHz, CDCl ) δ 8.37 (d, J = 7.7 Hz, 1H), 7.87 (dd, J = 75 = 7.5 Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.73 – 7.63 (m, 1H), 7.52
3
2
0.9, 6.6 Hz, 4H), 7.64 (dt, J = 21.9, 7.4 Hz, 2H), 7.55 (dd, J =
(q, J = 5.3 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 2.51 (d, J = 0.6 Hz,
13
13
12.8, 6.5 Hz, 4H), 6.82 (d, J = 8.4 Hz, 2H), 3.76 (s, 3H).
C
1H). C NMR (126 MHz, CDCl ) δ 152.46, 149.41, 140.55,
3
NMR (126 MHz, CDCl ) δ 163.21, 152.75, 149.02, 139.16,
139.83, 138.46, 137.09, 134.91, 132.15, 131.31, 130.53, 129.58,
128.98, 127.89, 124.12, 123.63, 123.21, 117.17, 12.35. HRMS
80 (ESI+): Calculated for C H N O S : [M+H]+ 427.0336, Found
3
1
5
3
34.23, 133.81, 131.95, 130.54, 129.16, 123.75, 116.92, 113.87,
+
5.57. HRMS (ESI+): Calculated for C H N O S: [M+H]
1
9
16
2
3
21 15
2
2 2
53.0954, Found 4353.0419.
426.9721.
(
(
E)-1-(2-((3-nitrophenyl)sulfonyl)phenyl)-2-phenyldiazene.
(E)-methyl3-((2-(phenyldiazenyl)phenyl)sulfonyl)thiophene-2-
3f)
carboxylate. (3k)
85 Obtained as a pale yellow solid in 73% yield; M.p. 92ꢀ93 C. H
o
1
o
1
Obtained as a yellow solid in 63% yield; M.p. 162ꢀ163 C.
H
NMR (500 MHz, CDCl ) δ 8.92 (s, 1H), 8.46 (d, J = 7.8 Hz, 1H),
NMR (500 MHz, CDCl ) δ 8.54 (dd, J = 5.6, 3.6 Hz, 1H), 7.85 (d,
3
3
8.32 (d, J = 8.1 Hz, 1H), 8.23 (d, J = 7.8 Hz, 1H), 7.79 (dd, J =
J = 5.2 Hz, 1H), 7.79 – 7.71 (m, 1H), 7.68 – 7.61 (m, 1H), 7.49 (d,
1
3
3
7
.1, 2.1 Hz, 2H), 7.77 – 7.68 (m, 2H), 7.64 (d, J = 7.8 Hz, 1H),
.56 (ddd, J = 9.7, 5.2, 4.3 Hz, 4H). C NMR (126 MHz, CDCl3)
J = 7.6 Hz, 1H), 7.39 (d, J = 5.3 Hz, 1H), 3.71 (s, 1H). C NMR
1
3
(126 MHz, CDCl ) δ 159.44, 154.45, 152.40, 151.33, 146.00,
3
δ 152.48, 148.85, 147.95, 144.55, 137.37, 135.39, 133.71, 132.55, 90 145.89, 139.06, 134.18, 132.02, 131.79, 130.11, 130.09, 128.90,
1
30.89, 130.09, 129.61, 129.39, 127.50, 123.75, 123.59, 117.29.
123.69, 116.34, 52.59. HRMS (ESI+): Calculated for
C H N O S : [M+H]+ 387.0468, Found 386.9885.
+
HRMS (ESI+): Calculated for C H N O S: [M+H] 368.07,
1
8
13
3
4
18 14
2
4 2
Found 368.0146.
(
E)-1-phenyl-2-(2-(phenylsulfonyl)phenyl)diazene. (3l)
o
(
(
E)-1-(2-(naphthalen-2-ylsulfonyl)phenyl)-2-phenyldiazene.
95 Obtained as a orange solid in90% yield; M.p. 149ꢀ150 C.
1
3g)
H NMR (500 MHz, CDCl
.95 (dt, J = 6.3, 2.0 Hz, 2H), 7.83 – 7.75 (m, 2H), 7.68 (dtd, J =
22.5, 7.5, 1.5 Hz, 2H), 7.62 – 7.58 (m, 1H), 7.54 – 7.50 (m, 3H),
3
) δ 8.43 (dd, J = 7.8, 1.5 Hz, 1H),
o
7
Obtained as a pale yellow solid in 84% yield; M.p. 139ꢀ140 C.
1
H NMR (500 MHz, CDCl ) δ 8.64 (s, 1H), 8.64 (s, 1H), 8.57 –
3
1
3
7
.49 – 7.45 (m, 1H), 7.37 (dd, J = 10.6, 4.9 Hz, 2H). C NMR
8
7
–
.44 (m, 1H), 8.57 – 8.46 (m, 1H), 7.86 (dd, J = 22.7, 8.8 Hz, 3H),
.78 (d, J = 8.1 Hz, 3H), 7.70 (ddd, J = 9.2, 6.0, 1.8 Hz, 2H), 7.64
7.57 (m, 2H), 7.57 – 7.47 (m, 4H). C NMR (126 MHz, CDCl3)
1
00 (126 MHz, CDCl ) δ 146.56, 143.29, 142.32, 138.53, 134.56,
3
1
3
132.96, 132.04, 130.59, 129.46, 129.11, 128.66, 128.05, 123.77,
1
3
16.92. HRMS (ESI+): Calculated for C H N O S : [M+H]+
56.0395, Found 357.0432.
18 14 2 4 2
δ 152.72, 149.00, 138.98, 138.59, 134.97, 134.59, 132.01, 131.95,
1
1
30.63, 130.19, 129.46, 129.17, 129.11, 128.96, 127.87, 127.36,
23.76, 123.03, 116.89. HRMS (ESI+): Calculated for
1
05 (E)-1-(2-((4-chlorophenyl)sulfonyl)phenyl)-2-phenyldiazene.
C H N O S: [M+H]+ 373.1005, Found 373.0445.
(3m)
2
2
16
2
2
o
Obtained as a orange solid in 82% yield; M.p. 170ꢀ171 C.
1
H NMR (500 MHz, CDCl ) δ 8.40 (dd, J = 7.8, 1.4 Hz, 1H),
(E)-3,5-dimethyl-4-((2-(phenyldiazenyl)phenyl)sulfonyl)isoxaz
3
7
.93 – 7.86 (m, 2H), 7.84 – 7.76 (m, 2H), 7.71 (td, J = 7.6, 1.5 Hz,
ole. (3h)
o
1
110 1H), 7.65 (td, J = 7.6, 1.4 Hz, 1H), 7.63 – 7.58 (m, 1H), 7.57 –
Obtained as a white solid in 90% yield; M.p. 101ꢀ102 C. H
13
7
.51 (m, 3H), 7.37 – 7.30 (m, 2H). C NMR (126 MHz, CDCl3)
δ 152.65, 148.94, 140.76, 139.61, 138.19, 134.79, 132.17, 130.68,
29.69, 129.40, 129.20, 128.95, 123.65, 117.03. HRMS (ESI+):
Calculated for C H N O S : [M+H]+ 322.0776, Found
NMR (500 MHz, CDCl ) δ 8.37 (d, J = 7.9 Hz, 1H), 7.77 (t, J =
3
7
.6 Hz, 1H), 7.73 – 7.65 (m, 3H), 7.56 (dd, J = 12.3, 7.0 Hz, 4H),
1
1
3
2.50 (s, 3H), 2.19 (s, 3H). C NMR (126 MHz, CDCl ) δ 174.00,
3
18
14
2
4 2
1
1
57.64, 152.98, 149.64, 137.80, 135.01, 132.19, 130.43, 129.24,
29.13, 123.30, 117.89, 117.64, 13.04, 10.81. HRMS (ESI+):
1
15 323.0832.
(
E)-1-(2-((4-(tert-butyl)phenyl)sulfonyl)phenyl)-2-phenyldiaze
ne. (3n)
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DOI: 10.1039/C5RA06474K
o
1
Obtained as a orange solid in 91% yield; M.p. 140ꢀ141 C.
60 H NMR (500 MHz, CDCl
3
) δ 8.39 (dd, J = 7.7, 1.5 Hz, 1H),
1
H NMR (500 MHz, CDCl ) δ 8.41 (dd, J = 7.7, 1.5 Hz, 1H),
.87 – 7.83 (m, 2H), 7.81 – 7.74 (m, 2H), 7.70 – 7.60 (m, 2H),
.57 – 7.54 (m, 1H), 7.53 – 7.49 (m, 3H), 7.38 – 7.32 (m, 2H),
7.85 (d, J = 8.3 Hz, 2H), 7.70 – 7.61 (m, 2H), 7.58 (dd, J = 7.7,
1.4 Hz, 1H), 7.50 – 7.42 (m, 2H), 7.37 (dd, J = 5.0, 3.1 Hz, 1H),
3
7
7
13
7.17 (d, J = 8.0 Hz, 2H), 7.12 – 7.07 (m, 1H). C NMR (126
MHz, CDCl ) δ 160.42, 149.01, 143.93, 139.37, 138.70, 137.02,
52.66, 149.13, 139.31, 138.77, 134.40, 131.98, 130.54, 129.28, 65 134.38, 130.58, 129.80, 129.46, 129.35, 128.12, 118.76, 117.98,
29.07, 127.89, 125.71, 123.78, 116.92, 35.08, 31.00. HRMS
116.93, 106.76, 55.56, 21.55. HRMS (ESI+): Calculated for
S: [M+H]+ 367.1111, Found 367.0548.
1
3
5
1.22 (d, J = 3.3 Hz, 9H). C NMR (126 MHz, CDCl ) δ 156.81,
3
3
1
1
(
ESI+): Calculated for C H N O S : [M+H]+ 378.1402, Found
C H N O
20 18 2 3
1
8
14
2
4 2
3
79.1446.
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
(E)-1-(5-methoxy-2-tosylphenyl)-2-phenyldiazene.(3t)
70 Obtained as a orange solid in 71 % yield; M.p. 70ꢀ71 C. H
o
1
(
E)-1-(4-methyl-2-tosylphenyl)-2-(p-tolyl)diazene. (3o)
o
1
Obtained as a orange solid in 86% yield; M.p. 174ꢀ175 C. H
NMR (500 MHz, CDCl ) δ 8.23 (s, 1H), 7.87 (d, J = 8.3 Hz, 2H),
.74 (d, J = 8.2 Hz, 2H), 7.55 (d, J = 8.1 Hz, 1H), 7.47 (dd, J =
8.1, 1.1 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.19 (d, J = 8.1 Hz,
NMR (500 MHz, CDCl ) δ 8.32 (d, J = 8.7 Hz, 1H), 7.84 – 7.79
3
(m, 4H), 7.55 – 7.50 (m, 3H), 7.15 (d, J = 8.1 Hz, 2H), 7.12 –
3
13
7
7.07 (m, 2H), 3.89 (s, 3H), 2.31 (s, 3H). C NMR (126 MHz,
CDCl ) δ 164.13, 152.57, 150.71, 143.54, 140.00, 132.05, 131.36,
3
1
3
2
H), 2.54 (s, 3H), 2.48 (s, 3H), 2.34 (s, 3H). C NMR (126 MHz, 75 131.11, 129.23, 129.12, 127.94, 123.84, 116.15, 101.22, 55.97,
CDCl ) δ 150.91, 147.03, 143.72, 142.46, 141.26, 139.60, 138.53, 21.51. HRMS (ESI+): Calculated for C H N O S: [M+H]+
3
20 18
2
3
1
2
34.88, 129.73, 129.62, 129.23, 128.14, 123.73, 116.73, 21.61,
1.53, 21.45. HRMS (ESI+): Calculated for C H N O S:
[M+H]+ 365.1318, Found 365.076.
367.1111, Found 367.0548.
2
1
20
2
2
(E)-1-(5-methoxy-2-tosylphenyl)-2-(m-tolyl)diazene.(3u)
o
1
8
0
Obtained as a orange solid in 81% yield; M.p. 70ꢀ71 C. H NMR
(
E)-1-(5-methyl-2-tosylphenyl)-2-(m-tolyl)diazene. (3p)
Obtained as a white solid in 75% yield; M.p. 96ꢀ97 C. H NMR
500 MHz, CDCl ) δ 8.30 (d, J = 8.1 Hz, 1H), 7.86 (d, J = 8.3 Hz,
(500 MHz, CDCl ) δ 8.32 (d, J = 8.8 Hz, 1H), 7.83 (d, J = 8.3 Hz,
3
o
1
2H), 7.65 (d, J = 7.8 Hz, 1H), 7.58 (s, 1H), 7.41 (t, J = 7.7 Hz,
1H), 7.34 (d, J = 7.5 Hz, 1H), 7.17 (d, J = 8.3 Hz, 2H), 7.10 (dd, J
= 8.8, 2.6 Hz, 1H), 7.07 (d, J = 2.6 Hz, 1H), 3.89 (s, 3H), 2.47 (s,
(
3
2H), 7.67 (d, J = 7.9 Hz, 1H), 7.60 (s, 1H), 7.48 – 7.40 (m, 2H),
13
7
.40 – 7.32 (m, 2H), 7.20 (d, J = 8.1 Hz, 2H), 2.48 (d, J = 10.1 85 3H), 2.33 (s, 3H). C NMR (126 MHz, CDCl ) δ 164.14, 152.67,
3
1
3
Hz, 6H), 2.35 (s, 3H). C NMR (126 MHz, CDCl ) δ 152.80,
49.06, 145.57, 143.66, 139.72, 138.95, 135.91, 132.69, 130.96,
29.45, 129.24, 128.92, 128.04, 123.82, 121.45, 117.18, 21.62,
21.54, 21.38. HRMS (ESI+): Calculated for C H N O S:
M+H]+ 365.1318, Found 365.0756.
150.79, 143.48, 140.06, 138.98, 132.84, 131.35, 130.95, 129.22,
128.92, 127.89, 123.93, 121.57, 116.04, 101.19, 55.95, 21.53,
21.37. HRMS (ESI+): Calculated for C H N O S: [M+H]+
3
1
1
21
20
2
3
381.1267, Found 381.0685.
2
1
20
2
2
[
90
(
(
E)-1-(4-ethoxy-2-tosylphenyl)-2-(4-ethoxyphenyl)diazene.
3q)
Obtained as a white solid in 83% yield; M.p. 95ꢀ96 C. H NMR
Acknowledgments
This work was supported by the Zhejiang Provincial Natural
Science Foundation of China (No. LZ13B020001), National
o
1
(
2
500 MHz, CDCl ) δ 7.91 (d, J = 2.7 Hz, 1H), 7.86 (d, J = 8.3 Hz, 95 Natural Science Foundation of China (No. 21376058) and Major
3
H), 7.79 (d, J = 8.9 Hz, 2H), 7.69 (d, J = 8.9 Hz, 1H), 7.19 (d, J
8.1 Hz, 2H), 7.16 – 7.13 (m, 1H), 7.02 – 6.99 (m, 2H), 4.23 (q,
J = 7.0 Hz, 2H), 4.16 (d, J = 7.0 Hz, 2H), 2.34 (s, 3H), 1.52 (d, J
scientific and technological innovation projects of Hangzhou City
(No. 20122511A43).
=
1
3
= 6.9 Hz, 3H), 1.49 (d, J = 6.9 Hz, 3H). C NMR (126 MHz,
CDCl ) δ 161.77, 160.33, 147.13, 143.71, 142.76, 140.11, 139.61,
29.22, 128.07, 125.53, 120.75, 118.35, 114.60, 113.75, 64.55,
3.90, 21.53, 14.77, 14.65. HRMS (ESI+): Calculated for
3
1
00 Notes and references
1
6
1
(a) G. Y. Song, F. Wang and X. W. Li, Chem. Soc. Rev. 2012, 41,
+
C H N O S: [M+H] 425.153, Found 425.0923.
2
3
24
2
4
3651ꢀ3678. (b) Y. Fall, H. Doucet and M. Santelli. Chem. Sus. Chem.
2
2
009, 2, 153ꢀ157. (c) H. Y. Fu, L. Chen and H. Doucet. J. Org. Chem.
012, 77, 4473ꢀ4478. (d) A. M. Sajith, A. Muralidharan. Tetrahedron Lett.
(
(
E)-1-(5-methoxy-2-tosylphenyl)-2-(3-methoxyphenyl)diazene.
3r)
Obtained as a orange solid in 85% yield; M.p. 139-140 C. H
NMR (500 MHz, CDCl ) δ 8.33 (d, J = 8.7 Hz, 1H), 7.85 (d, J =
8.3 Hz, 2H), 7.55 – 7.49 (m, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.41 –
.38 (m, 1H), 7.18 (d, J = 8.1 Hz, 2H), 7.14 – 7.08 (m, 3H), 3.93
s, 3H), 3.90 (s, 3H), 2.33 (s, 3H). C NMR (126 MHz, CDCl ) δ
3
64.15, 160.33, 153.79, 150.71, 143.56, 140.06, 131.45, 130.97,
29.82, 129.31, 127.80, 118.86, 118.10, 116.19, 106.73, 101.29,
1
05 2012, 53, 5206ꢀ5210. (e) A. M. Sajith, A. Muralidharan.Tetrahedron Lett.
o
1
2
012, 53, 1036ꢀ1041. (f) H. Cao, Y. G. Lin, H. Y. Zhan, Z. D. Du, X. L.
3
Lin, Q. M. Liang and H. Zhang. RSC Adv. 2012, 2, 5972ꢀ5975. (g) A.
Nova, R. MasꢀBalleste and A. Liedos, Organometallics. 2012, 31,
7
(
1
1
1
245ꢀ1256. (h) Y.S. Qiu, Y.Y. Kuang and J. Wu, Adv. Synth. Catal. 2014,
110 356(17), 3483ꢀ3504.
(a) C. P. David, A. L. Matthias, Geibel, E. M. N. Johannes, Klein and
1
3
2
R. Tobias, J. Am. Chem. Soc. 2009, 131, 17050ꢀ17051. (b) M. Joy,
Racowski, R. D. Allison and S. S. Melanie, J. Am. Chem. Soc. 2009,
55.98, 55.56, 21.51. HRMS (ESI+): Calculated for C H N O S:
2
1
20
2
4
[
M+H]+ 397.1217, Found 397.0627.
1
31,10974ꢀ10983.
115 3 Z. Y. Wu, H. Y. Song, X. L. Cui, C. Pi, W. W. Du and Y. J. Wu, Org.
Lett. 2013, 15(6), 1270ꢀ1273.
4 P. M. Liu and G. F.Christopher, Org. Lett. 2013, 15( 22)，5862ꢀ5865
(
E)-1-(3-methoxyphenyl)-2-(2-tosylphenyl)diazene. (3s)
o
Obtained as a orange solid in 15% yield; M.p. 73-74 C.
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DOI: 10.1039/C5RA06474K
5
H. Sun, C. M. Wang, Y. F. Yang, P. Chen, Y. D. Wu and X. H. Zhang,
(
b) C. Shen, J. Xu, W. B. Yu and P. F. Zhang, Green Chem. 2014, 16,
J. Org. Chem. 2014, 79(24):11863ꢀ72.
6
2
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