Arenesulfonyl Fluoride Synthesis via Copper-free Sandmeyer-type Fluorosulfonylation of Arenediazonium Salts

Article abstract of DOI:10.1002/cjoc.202000175

The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further application in many research fields including medicinal chemistry and chemical biological, organic synthesis, polymer preparation, etc. We report herein a mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides using K₂S₂O₅ as both a reductant and a practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine source. This methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.

Full text of DOI:10.1002/cjoc.202000175

Chinese Journal
of Chemistry
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Title: Arenesulfonyl fluoride synthesis via copper-free Sandmeyer-type
fluorosulfonylation of arenediazonium salts
Authors: Qiongzhen Lin, Zhanhu Ma, Changge Zheng,* Xiao-Jun Hu,* Yong Guo,
Qing-Yun Chen, Chao Liu*
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This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000175.
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国 化 学 - An International Journal
Arenesulfonyl fluoride synthesis via copper-free Sandmeyer-type
fluorosulfonylation of arenediazonium salts
Qiongzhen Lin,c Zhanhu Ma,a Changge Zheng,*c Xiao-Jun Hu,*a Yong Guo,b Qing-Yun Chen,b Chao Liu*a,b
aSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, China
bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese
Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
cSchool of Chemical Engineering, Xinjiang Agricultural University, Urumqi, Xinjiang Uygur Autonomous Region 830052, China.
*E-mail: chaoliu@sit.edu.cn; cgzheng@jiangnan.edu.cn; hu-xj@mail.tsinghua.edu.cn
Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
Summary of main observation and conclusion The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further
application in many research fields including medicinal chemisty and chemical biological, organic synthesis, polymer preparation, etc.. We report herein a
mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides
using K2S2O5 as both a reductant and a practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine source. This
methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.
Background and Originality Content
arenesulfonyl chlorides that are relatively unstable and
moisture-sensitive (Scheme 1A).[1,3] Alternative starting
[4]
materials including ArSO2NHNH2
, , ,
ArSO2Na[5] ArSO3Na[6]
Since sulfonyl fluoride groups (SO2F) have unique properties
including special stability-reactivity pattern and
ArSSAr[7], ArSH[8], etc., have been successfully converted into
the desired corresponding arenesulfonyl fluorides using an
appropriate oxidant and fluorinating reagents (Scheme 1A). An
efficient synthesis of various arenesulfonyl fluorides by
palladium-catalyzed cross-coupling of aryl halides with
proton-mediated reactivity that is sensitive to the
micro-environment,[1] arenesulfonyl fluorides are highly
valuable synthetic motifs that have been adopted in a variety
of applications including the prominent sulfur fluoride
exchange (SuFEx) reaction for “click chemistry” pioneered by
Sharpless and co-workers,[1] attracting fast-growing attention
in the community of both chemical biologists and synthetic
organic chemists.[2] However, there are only limited synthetic
methods to efficiently access them, which seriously hinders
their further applications. The classical chloride-fluoride
exchange of arenesulfonyl chlorides for the synthesis of
corresponding arenesulfonyl fluorides requires preparation of
1,4-diazabicyclo[2.2.2]octane-bis(sulfur
dioxide)
adduct
(DABSO) in combination with electrophilic fluorinating
reagents has been developed recently (Scheme 1B).[9] Two
recent reports have demonstrated the synthesis of
arenesulfonyl fluorides via sulfuryl fluoride incorporation from
arynes or various Grignard reagents (Scheme 1C).[10] Despite
these advances, access to various arenesulfonyl fluoride from
inexpensive and wildly available starting material by a practical
and mild method is still highly desired.
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fluorosulfonylation, we report herein copper-free Sandmeyer-type
fluorosulfonylation of various arenediazonium salts with the use
of N-fluorobenzenesulfonimide (NFSI) as an efficient fluorine
source and K2S2O5 as an inexpensive and practical sulfonyl source
Scheme
1
Established synthetic methods for arenesulfonyl
fluorides
(Scheme 2)[22]
.
,
,
an
1
Pd /lig
]
d
DABSO
(
) [
r
-
,
i P OH 75 o
C
.
e c
t
,
,
X
R
e ec uor
tfl
X
KF
S
l
DAST
or e ec uor
R
2
NFSI
S
l
tfl
(
)
X
S
-
-
A
B
( )
Y
(
)
ass ca
Cl
l Cl F
,
Cl NHNH2
or ox
exc an
e
g
ross cou
C
n
pli
g
i
h
,
=
r
B I
Scheme 2 Arenesulfonyl fluoride synthesis from arenediazonium
,
,
=
=
,
X
i
( )
X
O
Y
a
ve uor na on
id ti fl i
ti
,
a
N
a
ON SR
,
,
SA
=
or w o
/
r
ii
( )
X
Y
H
R
salts via radical SO2 insertion and fluorination strategy
SO2F
-
F
R
X
Y
OTf
MgB
+ or
"
", "
"
R
SO2F2
g
)
SO2
F
(
D
( )
-
C
(
)
N2+BF4
nco ra on
ti
SO2F2 i
n
se
i
r
a
R
ca
o
n
p
d
i
l
ti
SO2
,
,
=
=
=
i
X
TMS
Y
X
an
uor na on
d fl
i
ti
ur s ra e
t
gy
( )
or w o
r or
MgI
SO2
N
SO2
N
ii
( )
/
Y
O
t
KHF2
/
DABSO
(
)
-
-
-
, '
.
ca
, '
C Cl2/6 6 di
u
me
r
thyl 2 2 dipy idyl
t
)
(
,
,
r
e
M CN t 12 h
rev ous wor
k
p
i
R
R
F
SO2
N2BF4
s wor
thi
k
The Sandmeyer reaction has been widely used for the conversion
of aromatic amino groups into a variety of functional groups, such
as halogen, hydroxyl, cyano, boryl groups etc.[11] Recently
Sandmeyer-type fluoroalkylation of arenediazonium salts has
been developed, and various fluorine-containing functional
PhO2S
PhO2S
-
F
N
K
2S2O5
/
NFSI
(
)
,
,
e
c r
M CN/H2O/HOA t 6 h
[12]
[13]
groups
including
CF3
,
SCF3
,
SCF2H[14]
,
CF2H[15]
can be
,
Results and Discussion
[16]
[18]
CF2HSO2/CH2FSO2
,
CnF2n+1 (n>2)[17] and OCF3
Our initial studies on the Sandmeyer-type fluorosulfonylation
arenediazonium salts were carried out using
efficiently incorporated into arenes. Moreover, clorosulfonylation
of arenediazonium salts has been achieved as well.[19] However, to
our best knowledge, the corresponding Sandmeyer-type
fluorosulfonylation reaction of arenediazonium salts has never
been reported such far. We conceived that the combination of
economical SO2 and an appropriate fluoride source would achieve
it via radical SO2 insertion and fluorination strategy (Scheme 1D).
Based on this new strategy, we have already developed an
efficient method for the preparation of a number of alkyl sulfonyl
fluorides.[20] Very recently, we have established the first synthesis
of various arenesulfonyl fluorides from arenediazonium salts in
combination of KHF2 as a fluorine source and SO2 surrogate
1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct (DABSO)
as a sulfonyl source via copper-catalyzed radical SO2 insertion and
fluorination strategy (Scheme 2).[21] As a good complement to this
method and as a continuation of our research interest in
of
p-methoxybenzenediazonium salt 1a as the model substrate,
DABSO as a popular and commercially available solid SO2
source[23], and NFSI as a fluoride source. As shown in Table 1,
initial experiments revealed that the combination of 2.0 equiv of
DABSO, 1.0 equiv of NFSI in MeCN at room temperature for 6
hours did not efficiently generate the desired arenesulfonyl floride,
and only trace amounts of the product 2a were detected (entry 2).
Careful analysis of the reaction mixture demonstrated that the
majority of starting arenediazonium salt 1a was not consumed.
Then UV irradiation or copper powder was used to improve the
reaction, and increased yields of the desired product were
observed (entries 3 and 4). It is well-known that K2S2O5 can be
used as both good inorganic SO2 surrogate[24] and effective
reductant. It was found that the desired reaction was improved
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Running title
Chin. J. Chem.
when DABSO was replaced with K2S2O5 (entry 5). Notably, water
had positive effect on the reaction and good yield of the desired
product 2a was obtained in its presence (entry 6). To our delight,
when HOAc was used as co-solvent, the desired reaction was
further improved and a good yield of 80% was achieved (entry 1),
which might be ascribed to the suppression of formation of
undesired products by HOAc including Sandmyer-type or azo
byproducts. Interestingly, lower yield of the product was observed
in the absence of water (entry 7), thus demonstrating the key role
of water in the desired Sandmeyer-type fluorosulfonylation
reactions probably by increasing the solubility of K2S2O5 in the
reaction mixture. The utilization of Selectfluor as electrophilic
fluorine source was not effective for the transformation and
obvious drop in the yield of the desired product was observed
(entry 8). Furthermore, the increased concentration of K2S2O5 or
NFSI did not have a significant effect on the reaction (entries 9
and 10). These extensive screening of reaction conditions showed
that the combination of 2.0 equiv of K2S2O5 and 1.0 equiv of NFSI
in MeCN/H2O/HOAc at room temperature for 6 hours provided
optimal reaction conditions to generate the desired
fluorosulfonylation product in good yield (entry 1).
4
DABSO instead of K2S2O5, MeCN,
UV irradiation
8
5
6
7
8
9
without HOAc and H2O
without HOAc
35
56
45
57
80
78
without H2O
Selectfluor instead of NFSI
2.0 equiv of NFSI
10
4.0 equiv of K2S2O5
a
General reaction conditions: arenediazonium salt (1a, 0.2
mmol), K2S2O5 (0.4 mmol), NFSI (0.2 mmol) in MeCN/H2O/HOAc
(3/0.05/0.2 mL) under Ar atmosphere at room temperature for 6
hours. Yields were determined by 19F NMR spectroscopy using
b
1-methoxy-4-(trifluoromethoxy)benzene as an internal standard.
With the optimal reaction conditions in hand, we next
engaged in examining the generality of this copper-free
Sandmeyer-type fluorosulfonylation of various arenediazonium
salts and the results are summarized in Table 2. A wide range of
arenediazonium salts with electron-donating, neutral, and
electron-withdrawing substituents were smoothly transformed
into the corresponding Sandmeyer-type fluorosulfonylation
products in good yields. As expected, no fluorinated byproducts
were formed in these reactions, but some polar and complicated
Sandmeyer-type or azo byproducts were observed. Thanks to the
mild reaction conditions employed, a series of functional groups
including ether (2a-e), ester (2f-i), halogen (2j, 2k), cyano (2l),
nitro (2m), sulfonyl (2n) and hydroxyl (2o) were well tolerated
under the reaction conditions providing the corresponding target
products in good yields. In particular, the substrate 1o bearing an
active OH group delivered the corresponding products in good
yields. However, it was found that heteroarenediazonium salts 2w
and 2x are not suitable reaction partners for the current
Table 1 Optimization of reaction conditionsa
PhO
2S
-
e
c
F
N
M
CN/H2O/HOA
PhO2S
e
e
M
O
N2BF4
u v
K
2S2O5
F
SO2
M
O
,
r
NFSI
t
6 h
(
)
u v
i
.
.
.
a
1
a
2
e
q
e
u v
q
e
1 0
i
2 0
i
1 0
q
Entry
Variation from the standard Yield of 2a (%)b
conditions
1
2
3
none
80
DABSO instead of K2S2O5, MeCN
trace
DABSO instead of K2S2O5, MeCN, 32
1.0 equiv of Cu
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Report
e
transformation and lower yields of the corresponding
fluorosulfonylation products were formed. Furthermore,
gram-scale synthesis of 2a was performed on 8.0 mmol scale to
estimate practicality of this reaction and a good yield of the target
product was obtained, thus demonstrating good viability of the
transformation for scale-up.
OM
SO2F
SO2F
SO2F
SO2F
6%
e
M
O
EtO
O
2d
a
c
6
7
2
7
2b 4
2
0%
%
6
5
%
.
,
mmo sca e
78 8 0
%
l
l
)
(
SO2F
SO2F
SO2F
EtOOC
SO2F
O
EtO2C
EtO2C
e
2
7
8%
2f 44
2g 54
2h 5
3%
%
%
SO2F
SO2F
SO2F
SO2F
O
r
B
F
NC
O
b
2i
2
7
2k 4
8%
2l
2p
2t
58
38%
5
68%
%
%
j
(
)
SO2F
SO2F
SO2F
O2N
SO2F
e
M
O2S
t
u
B
HO
m
2
n
2
o
53
35%
SO2F
44
%
2
%
61%
Table 2 Substrate scope for the copper-free Sandmeyer-type
SO2F
SO2F
fluorosulfonylation of various arenediazonium saltsa
SO2F
e
M
b
r
2
s
4
8
2q
7
(
2
55
%
9
60%
55
%
%
%
)
SO2F
SO2F
N
O
SO2F
S
SO2F
)
e
e
M
e
M
OM
b
x
2
1
3%
(
u
2
v
2
w
2
7
9%
6
4
%
9%b
(
)
N2BF4
SO2F
e
c
M CN/H2O/HOA
PhO2S
PhO2S
-
R
R
a Standard reaction conditions: arenediazonium salt (0.3 mmol),
K2S2O5 (0.6 mmol), NFSI (0.3 mmol) in MeCN/H2O/HOAc
(4.5/0.075/0.3 mL) under Ar atmosphere at room temperature
K2S2O5
F
N
,
r
t 6 h
1
2
NFSI
(
)
b
for 6 hours. Yields of isolated products are given. Yields were
determined
by
19F
NMR
spectroscopy
as an
using
1-methoxy-4-(trifluoromethoxy)benzene
standard.
internal
Some
preliminary
mechanistic
studies
on
the
Sandmeyer-type fluorosulfonylation of arenediazonium salts were
carried out in order to gain some insights into the reaction
pathway. First, 2,2,6,6-tetramethyl-1-piperidyloxy (TEMPO) as a
radical scavenger was added to the reaction of 1a, resulting in an
obvious decrease in the yield and successful observation of the
corresponding TEMPO-trapped complex 3 (Scheme 3a). Second,
arenediazonium salt 4 was subjected to the standard reaction
conditions to generate the ring-closed product 5 in 23% isolated
yield (Scheme 3b). This might be ascribed to the fact that the alkyl
radical generated in situ from addition of aryl radical to the
alkenyl group in
4 undergoes irreversible intramolecular
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Running title
Chin. J. Chem.
cyclization at a much fast rate than that of the consequent aryl
radical SO2 insertion. All these results strongly demonstrate the
radical character of the reaction. Based on the above
experimental results and literature,[25] we propose the following
reaction pathway for the desired copper-free Sandmeyer-type
further application in different fields. Further studies on the
synthesis of other sulfonyl fluorides via the radical SO2 insertion
and fluorination strategy are in progress.
Experimental
fluorosulfonylation
reaction
of
arenediazonium
salts.
Arenediazonium salt 1 readily generates the corresponding aryl
radical by K2S2O5 via a single electron transfer (SET) process under
the reaction conditions. It is rapidly trapped by SO2 originated
General Procedure for the Sandmeyer-type fluorosulfonylation
of arenediazonium salts. Arenediazonium salt 1 (0.3 mmol),
K2S2O5 (133.2 mg, 0.6 mmol) and NFSI (94.5 mg, 0.3 mmol) were
added to a sealed tube. The system was then evacuated and
backfilled with Ar (3 times) and distilled CH3CN (4.5 mL), H2O (75
μL) and HOAc (0.3 mL) were added in turn via syringe under Ar
atmosphere. The reaction mixture was sealed and stirred at room
temperature for 6 hours. Yields of the desired product were
measured by 19F NMR spectroscopy before working-up. Then the
reaction mixture was filtered through a pad of celite, diluted with
DCM (20 mL) and H2O (50 mL). The resulting mixture was
extracted with DCM (2 × 20 mL). The organic layers were
combined, washed with brine (50 mL), dried over Na2SO4, filtered
and concentrated. The crude product was purified by silica gel
chromatography to give the desired product.
.
from K2S2O5 to form the corresponding [ArSO2 ] intermediate, and
their subsequent rapid fluorination by NFSI results in the desired
arenesulfonyl fluoride 2 (Scheme 3c).
Scheme
copper-free
arenediazonium salts
3
Preliminary mechanistic investigation of the
Sandmeyer-type
fluorosulfonylation
of
on ro ex er men s:
C
t
l
p
i
t
SO2F
N2BF4
e
M
c
CN/H2O/HOA
O
PhO2S
PhO2S
-
N
K2S2O5
F
N
a
,
(
)
r
t
6 h
e
e
M
O
M
O
e
OM
NFSI
(
)
a
a
1
2
3
19
e
F NMR yi ld
80%
--
no a
ve
dditi
.
-
e
u v
q
o serve
b
1 0
i
TEMPO
d by GC MS
39%
O
O
e
M
c
O
CN/H2O/HOA
PhO2S
PhO2S
-
b
(
)
K2S2O5
F
N
,
r
t
6 h
N2BF4
SO2F
NFSI
(
SO2F
)
no
o serve
b d
so a e
e
d y
i
4
5
i
l
t
l
d
t
23
%
ro ose reac on
a
wa :
P
p
d
ti
p
th
y
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
PhO2S
PhO2S
-
F
N
c
K2S2O5
(
)
K2S2O5
NFSI
(
)
r
A
r
r
A
r
F
N2BF4
A SO2
A SO2
2
1
Conclusions
Acknowledgement (optional)
In conclusion, based on the radical SO2 insertion and
fluorination strategy, we have developed copper-free
The authors gratefully acknowledge the financial support
from the National Natural Science Foundation of China (Nos.
21421002, 201871283, 21737004, 21672239), Science and
Technology Commission of Shanghai Municipality (No.
17ZR1437000), and the Foundation of Science and Technology on
Sanming Institute of Fluorochemical Industry (FCIT201701BR).
a
Sandmeyer-type fluorosulfonylation reaction of readily available
arenediazonium salts using cheap K2S2O5 as both a reductant and
a sulfonyl source and NFSI as an effective fluorine source. This
transformation permits a fast and facile construction of various
highly valuable arenesulfonyl fluorides from low-cost and widely
available starting materials, and is expected to greatly expand the
toolkit of arenesulfonyl fluorides and significantly promote their
Chin. J. Chem. 2019, 37, XXX－XXX
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First author et al.
Report
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
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© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Running title
Chin. J. Chem.
Entry for the Table of Contents
Page No.
Arenesulfonyl
fluoride
synthesis
via
e
c
H A
2O/ O
R
R
M
N H
/
C
Ph
Ph
O2S
-
copper-free
fluorosulfonylation of arenediazonium salts
Sandmeyer-type
K
2S2O5
F
SO2
N2BF4
F
N
,
r
O2S
t
h
6
NF
(
I
)
S
v
r n
m
r
a a a e s a
a e a
Wildly
il bl
t
ti
t
i l
g
ea
p K
as su on source
h
C
lf yl
2S2O5
o
er ree
C pp
f
an rac ca reac on con ons
Mild d p ti ti
diti
l
A
mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various
arenediazonium salts was developed to prepare valuable arenesulfonyl fluorides using K2S2O5 as a
practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine
source.
Qiongzhen Lin, Zhanhu Ma, Changge Zheng,*
Xiao-Jun Hu,* Yong Guo, Qing-Yun Chen, Chao
Liu*
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.