Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400

Article abstract of DOI:10.1039/c8nj00075a

Sulfonylation using stable and readily available arylsulfonyl hydrazides and aryl iodides or bromides mediated by cupric acetate has been achieved. Using polyethylene glycol (PEG-400) as an eco-friendly medium, the coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields without the presence of additional ligands and base.

Full text of DOI:10.1039/c8nj00075a

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Copper-mediated sulfonylation of aryl iodides and bromides with
arylsulfonyl hydrazides in PEG-400
Xiangmei Wu*, Yan Wanga
Received 00th January 20xx,
Accepted 00th January 20xx
The sulfonylation from stable and readily available arylsulfonyl hydrazides and aryl iodides or bromides mediated by cupric
acetate has been achieved. Using polyethylene glycol (PEG-400) as eco-friendly medium, the coupling reaction could
afford a series of unsymmetrical diaryl sulfones in moderate to good yields without the presence of additional ligand and
base.
DOI: 10.1039/x0xx00000x
www.rsc.org/
these above-mentioned methods.6 Advantageously, a
transition metal-free synthesis of diaryl sulfones from
Introduction
Aryl sulfone moieties are ubiquitous in many
biologically and pharmaceutically active molecules
which present potential antifungal, antibacterial, or
antitumor activities, and moreover, they also constitute
versatile building blocks in materials science and
organic synthesis.1 Conventional routes to aryl sulfones
mainly comprises the reaction of organometallic
reagents with sulfonate esters,2 the oxidation of
corresponding sulfides,3 the sulfonylation of suitable
arenes in the presence of strong acid with arylsulfonic
acids or arylsulfonyl halides,4 as well as the nucleophilic
substitution of alkyl halides with arylsulfinate salts.5
Every last the aforementioned strategy has its own
merit, however, disadvantages such as the limited
availability of precursors, the formation of mixtures of
isomeric, low compatibility of some functional groups
and harsh reaction conditions are usually supervened in
the most cases.
arylsulfinic acid salts and diaryliodonium salts was also
described.7 Furthermore, in the recent years, transition
metal-catalyzed direct sulfonylation via C-H bonds of
heteroaromatic compounds with sodium arylsulfinates
or arylsulfonyl chlorides were explored, possessing its
fascinating synthesis prospects.8
Nevertheless, the high cost of palladium catalyst
obviously restricts the practical utilization, and various
bases or relevant additives are often required in a
stoichiometric excess in most transition metal
complexes-catalyzed cases, which inevitably generate a
certain amount of wasteful byproducts that complicate
the isolation of desired products. In addition, the use of
air or moisture-sensitive sulfonylating reagents is
usually not avoidable or additional prefunctionalization
of the starting material like diaryliodonium salts is
concluded in the metal-free protocol. And most of all, it
is noteworthy that environmentally unfriendly solvents
such as DMF, DMSO or toluene are indispensability in
the above-mentioned works, which have a negative
impact on the environment under a larger scale process.
Undoubtedly, due to the extensive use of arylsulfones
and related scaffolds, improved methods catalyzed or
promoted by inexpensive and non-toxic copper
complexes under environmentally benign solvents for
the access to diaryl sulfones is still in demand.
Over the past few decades, palladium or copper-
catalyzed coupling of arylsulfinic acid salts or
arylsulfonyl chlorides with aryl halides and triflates as
well as arylboronic acids to synthesize aryl sulfones,
especially for unsymmetrical diaryl sulfones, were
developed as milder and more applicable alternatives to
Compared to conventional organic solvents, owing to
the traits of negligible vapour pressure, thermally
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stability,
biodegradability
and
non-toxicity, smaller alcohols such as ethyl alcohol, glycol and
polyethylene glycols (PEG) and their derivatives have glycerol give less satisfactory results (entries 7-9).
emerged as perfect medium for environmentally
9
Next, comparison of different copper sources
friendly and secure chemical reactions indisputably.
indicated that Cu(OAc)2·H2O promoted the reaction
On the other hand, it is well known that sulfonyl
effectively and provided a higher yield compared to the
hydrazides which exist as stable solids and being readily
other Cu(II) compounds tested, such as Cu(NO3)2·5H2O,
available as sulfonylation reagent theoretically produce
only N2 as byproduct.10 Therefore, based on our
CuSO4·5H2O, CuCl2·2H2O, CuBr2 and CuO (entries 10-
14). In addition, Cu(I) sources were also checked, and
previous report about the copper-mediated coupling
they could give relatively lower yields under the same
reaction between aryl boronic acids and aryl sulfonyl
hydrazides using EtOH as solvent 11, and considering
conditions (entries 15-17). However, almost no
anticipated product was observed when the other metal
that aryl iodides and bromides are readily accessible,
salts like Ni(OAc)2, Co(OAc)2 or FeCl3 was substituted
low cost and compatible with numerous functional
for copper salts (entries 18-20). Furthermore, with
groups, and especially, the impendency of the pursuit
regard to the quantity of Cu(OAc)2·H2O, 1.0 equiv. was
for the environmentally benign media, herein, we wish
found to be optimal as no significant increase in the
to report a mild and efficient route to diaryl sulfones
yield of desired product was observed with the use of
from arylsulfonyl hydrazides and aryl iodides or
more than 1.0 equiv of Cu(OAc)2·H2O and it resulted in
bromides using cupric acetate as promoter and
somewhat lower yield when less than 1.0 equiv. was
polyethylene glycol as an eco-friendly medium.
adopted (entries 21 and 22). A certain amount of
unsymmetrical
diaryl
sulfide,
definitely,
p-
Results and discussion
methoxyphenyl-p-tolyl sulfide, was obtained when
decreasing the stoichiometric amount of Cu(OAc)2·H2O
to 0.1equiv.. Control experiment carried out in the
absence of Cu(OAc)2·H2O completely failed and the
starting materials were isolated intact from the reaction
mixtures (entry 23). Generally, an external base was
found to be necessary or crucial for the preparation of
aryl sulfones in most previous examples, however, the
addition of bases like KOH, K2CO3 and Cs2CO3, did not
enhance the reaction efficiency in this protocol (entries
24-26). Moreover, the change from air to nitrogen
atmosphere did not increase the conversion, which
consequently makes it be manipulatively simple and
convenient. Raising the temperature to 120oC almost
gave no improvement of the expected product.
Therefore, 1.0 equiv. Cu(OAc)2·H2O in PEG-400 at 100
°C under air for 12 h served as the optimal conditions
for the synthesis of p-methoxyphenyl-p-tolyl sulfone
from p-toluenesulfonyl hydrazide and p-iodoanisole.
Initially, a model reaction between commercially
available p-toluenesulfonyl hydrazide and p-iodoanisole
was investigated using 10 mol% of Cu(OAc)2·H2O as
catalyst in combination with PEG-400 as solvent under
air at room temperature. However, almost no desired
cross-coupling product was detected. Further,
stoichiometric quantity of Cu(OAc)2·H2O (1.0 equiv.)
as reaction promoter was also unsuccessful. To our
delight, when the latter process was conducted at 60oC,
a certain amount of the target product and trace amount
of bis-p-tolyl sulfone derived from the undesired
homocoupling of p-toluenesulfonyl hydrazide were
determined by GC-MS analysis (Table 1, entry 1),
indeed, without the presence of p-iodoanisole, only bis-
p-tolyl sulfone was observed under the same conditions.
Raising the temperature to 100oC, the reaction
proceeded smoothly and the desired product was
isolated in 75% yield after 12 h (entry 2).
Table 1 Optimization of reaction conditionsa
Based on the result, the influence of PEG with
different chain lengths was examined in the presence of
1.0 equiv. of Cu(OAc)2·H2O at 100oC. The results
revealed that PEG with longer or shorter chain lengths
such as PEG-600, PEG-800 and PEG-200 did not
remarkably change the yields (entries 3-6), however, the
SO2NHNH2
O
O
S
I
additive
Solvent
100oC
+
H3CO
CH3
H3CO
CH3
2 | J. Name., 2012, 00, 1-3
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Entry
1c
Additive(1 eq.)
Solvent
PEG-400
PEG-400
PEG-200
PEG-600
PEG-800
PEG-1000
EtOH
Yield(%)b
Using the established optimal conditions, a series of
diaryl sulfones was obtained in moderate to good yields
from p-toluenesulfonyl hydrazide with a variety of
substituted aryl iodides as depicted in Table 2. It is
noteworthy that substrates having different electron-
donating and electron-withdrawing substituents such as
methyl, methoxy, methylthio, fluoro, chloro, bromo and
amino groups at para, meta or ortho position were all
efficiently coupled to afford the corresponding products
(3aa-3ar). In general, aryl iodides bearing electron-
withdrawing substituents produce the corresponding
products in good yields (eg. -F, Cl and Br), whereas the
use of aryl iodides containing electron-donating
substituents led to a slight decrease in the yield (eg. -
Me, -OMe, -SCH3 and NH2). Moreover, the same group
at ortho position affording in a modest yield illustrated
that this coupling reaction should be sensitive to
sterichindrance (3ad, 3ah, 3an, and 3ar). A heteroatom-
containing aryl iodides like 2-iodopyridine and 2-
iodothiophene also provided 65% and 55% isolated
yields for the corresponding diaryl sulfones (3as and
3at). Remarkably, bromo, chloro and fluoro substituent
on the phenyl ring of aryl iodides remained intact under
the standard reaction conditions, which could offer the
opportunity for further synthetic manipulations (3aj-
3aq).
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(NO3)2·5H2O
CuSO4·5H2O
CuCl2·2H2O
CuBr2
40
75
70
75
74
72
50
65
68
25
30
28
25
10
17
18
20
/
2
3
4
5
6
7
8
glycol
9
glycerol
10
11
12
13
14
15
16
17
18
19
20
21d
22e
23
24f
25g
26h
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
CuO
CuCl
CuBr
CuI
To gain more insight into the substrate scope of this
coupling reaction, several substitued arylsulfonyl
hydrazides with iodobeneze were further evaluated
under the optimal reaction conditions. It was shown that
no matter if the arylsulfonyl hydrazides possessing
electron-donating or electron-withdrawing functional
groups, they were all good coupling partners in this
transformation and afforded the desired products in
moderate to good yields (3ba-3bd). Similar to the
aforementioned results, the sulfonylhydrazide group
represented exclusive chemoselectivity over halide
group on the phenyl ring as leaving groups,
demonstrating the potential access to highly
functionalized targets by stepwise coupling.
Ni(OAc)2
Co(OAc)2
/
FeCl3
/
Cu(OAc)2·H2O
Cu(OAc)2·H2O
/
76
60
/
Cu(OAc)2·H2O
Cu(OAc)2·H2O
Cu(OAc)2·H2O
75
75
76
aReaction conditions: 1.2 mmol p-iodoanisole; 1.0 mmol p-
toluenesulfonyl hydrazide; 2.0 ml solvent; 100 oC, 12h, in air.
Further experiments show that bromobenzen was
inappropriate as materials for the present aryl sulfone
synthesis, however, aryl bromides with electron-
withdrawing substituents can be utilized for this
transformation, like p-fluorobromobenzen and p-
chlorobromobenzen, although gave still somewhat low
bIsolated
yield.
c60oC
dCu(OAc)2·H2O
(1.5eq.)
f
eCu(OAc)2·H2O (0.5eq.) KOH gK2CO3 hCs2CO3
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Table 2 Synthesis of diaryl sulfones from various aryl
Table 3 Synthesis of diaryl sulfones from various aryl
bromides with p-toluenesulfonyl hydrazidea,b,12
iodides with arylsulfonyl hydrazidea,b,12
SO2NHNH2
SO2NHNH2
O
O
O
O
O
S
S
I
Br
Cu(OAc)2·H2O
Cu(OAc)2·H2O
+
+
R2
R1
R1
R1
R1
PEG-400
100°C
PEG-400
100°C
R2
1
2
3
1
2
3
O
O
O
O
O
O
O
O
O
O
O
S
S
S
S
S
S
F
Cl
3aa 80%
3ab 78%
3ac 76%
3aa 18%
3aj 40(60)%
3al 45(68)%
O
O
O
S
O
O
O
aReaction conditions: 1.2 mmol aryl bromides; 1.0 mmol
arylsulfonyl hydrazide; 1.0 mmol Cu(OAc)2·H2O; 2.0 ml PEG-400;
100 oC, 12h, in air. bIsolated yield. c120 oC (in parentheses)
S
S
H3CO
3af 75%
3ad 66%
3ae 52%
O
O
S
O
O
O
O
S
S
yield (Table 3, 3aa, 3aj, and 3al). As for p-
bromoiodobenzen, except for the former desired product
(3ap), trace amount of p-iodophenyl-p-tolyl sulfone was
detected by GC-MS analysis. Furthermore, elevating the
reaction temperature to 120°C significantly improved
the reaction, thus affording the desired products in
acceptable yields (data in parentheses).
OCH3
3ah 60%
OCH3
SCH3
3ag 78%
3ai 72%
O
O
O
O
O
O
S
S
S
Cl
Cl
F
3aj 82%
3al 88%
F
3ak 75%
O
O
S
O
O
O
O
Due to the fact that free radical reactions mediated by
sulfonyl radicals have been reported by several
S
S
groups10c-e,g,h
, a radical trapping experiment was
Cl
Cl
O
Cl
3ao 83%
3am 83%
3an 65%
conducted. When radical inhibitor, such as 2,2,6,6-
tetramethylpiperidine-N-oxide (TEMPO, 2 equiv. based
on p-toluenesulfonyl hydrazide) or butylated
hydroxytoluene (BHT) was added into the reaction
system of p-toluenesulfonyl hydrazide and p-
iodoanisole, the efficiency of the transformation was
almost not affected, which suggested that a radical
process for this reaction might be ruled out. On the basis
of our experimental results and the previous
literatures13, a plausible reaction pathway for this
sulfonylation of arylsulfonyl hydrazides and aryl iodides
or bromides is illustrated in Scheme 1 although the
precise mechanism is still not clear currently.
O
O
O
O
O
S
S
S
Br
NH2
I
3ap 73%
3aq 66%
3ar 57%
O
N
O
O
O
O
O
S
S
S
S
3ba 80%
3at 55%
3as 65%
O
O
O
O
S
O
O
S
S
OCH3
Cl
F
3bb 82%
3bd 78%
3bc 75%
Cu(OAc)2
a Reaction conditions: 1.2 mmol aryl iodides; 1.0 mmol arylsulfonyl
hydrazide; 1.0 mmol Cu(OAc)2·H2O; 2.0 ml PEG-400; 100 oC, 12h,
in air. bIsolated yield.
Ar1-SO2CuOAc
Ar X
Ar1-SO2NHNH2
Ar1-SO2-Ar
N2
Ar1-SO2-Cu-Ar
Scheme 1 Plausible reaction pathway
4 | J. Name., 2012, 00, 1-3
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Conclusions
In summary, we have developed an efficient and facile
protocol for copper-mediated coupling of arylsulfonyl
hydrazides and aryl iodides or bromides. It is worth
noting that the reaction can proceeds smoothly with the
use of polyethylene glycol as an eco-friendly medium
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We are grateful for financial support from the Natural Science
Foundation of Zhejiang Province (No. LY18B020005) and the
National Natural Science Foundation of China (No. 21572094).
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DOI: 10.1039/C8NJ00075A
ARTICLE
Journal Name
and M.-C. Scherrmann, Green Chem., 2013, 15, 1016-1029; (j) M.-
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12 General procedure
Aryl halide (1.2 mmol), arylsulfonyl hydrazide (1.0 mmol), cupric
acetate (1.0 mmol), and PEG-400 (2.0 ml) were taken in a 25 ml
sealed tube. The reaction mixture was stirred at 100 oC for 12 hours
in air. Water (10 ml) was added and then the mixture was extracted
with EtOAc (4×10 ml). The extracts were combined and washed by
brine (3×15 ml), dried over MgSO4, filtered, and evaporated, and
purified by chromatography on silica gel to obtain the desired
products with ethyl acetate/hexane (v/v=1:3～1:10). The products
were characterized by their spectral and analytical data and
compared with those of the known compounds.
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and S. K. Tian, Chem. Eur. J., 2012, 18, 1582-1585.
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8NJ00075A
Copper-mediated sulfonylation of aryl iodides and bromides
with arylsulfonyl hydrazides in PEG-400
Xiangmei Wu* and Yan Wang
Abstract: The sulfonylation from aryl iodides or bromides and arylsulfonyl hydrazides
mediated by cupric acetate with polyethylene glycol (PEG-400) as eco-friendly
medium is successful.
.
SO2NHNH2
O
O
S
X
Cu(OAc)2—H2O
+
R2
R1
R1
PEGꢀ400
100°C
R2
X=I, Br