C-H bond sulfonylation of anilines with the insertion of sulfur dioxide under metal-free conditions

Article abstract of DOI:10.1039/c8cc03465f

C-H bond sulfonylation of anilines with the insertion of sulfur dioxide under metal-free conditions is described. 2-Sulfonylanilines are generated in moderate to good yields through a three-component reaction of anilines, DABCO·(SO₂)₂, and aryldiazonium tetrafluoroborates under mild conditions. No metal catalysts or additives are needed for this transformation. This direct C-H functionalization is highly efficient, and broad functional group tolerance is observed. A radical process is believed to be involved. In the reaction process, the arylsulfonyl radical and the tertiary amine radical cation generated in situ from DABCO·(SO₂)₂, and aryldiazonium tetrafluoroborate are the key intermediates. Additionally, the tertiary amine radical cation acts as the electron carrier through a single electron transfer process.

Full text of DOI:10.1039/c8cc03465f

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DOI: 10.1039/C8CC03465F
ARTICLE
C-H Bond sulfonylation of anilines with the insertion of sulfur
dioxide under metal-free conditions
Kaida Zhou,a Jun Zhang,a Lifang Lai,b Jiang Cheng,b Jiangtao Sun,b and Jie Wu*a,c
Received 00th January 20xx,
Accepted 00th January 20xx
C-H Bond sulfonylation of anilines with the insertion of sulfur dioxide under metal-free conditions is described. 2-
Sulfonylanilines are generated in moderate to good yields through a three-component reaction of anilines, DABCO·(SO2)2,
and aryldiazonium tetrafluoroborates under mild conditions. No metal catalyst or additives are needed in this
transformation. This direct C-H functionalization is highly efficient, and broad functional group tolerance is observed. A
radical process is believed to be involved. In the reaction process, arylsulfonyl radical and tertiary amine radical cation
generated in situ from DABCO·(SO2)2, and aryldiazonium tetrafluoroborate are the key intermediates. Additionally, tertiary
amine radical cation acts as the electron carrier through a single electron transfer process.
DOI: 10.1039/x0xx00000x
www.rsc.org/
through ortho C(sp2)–H bond functionalization. In the past few
years, the insertion of sulfur dioxide into small molecules has
been recognized as an efficient route for the access to diverse
Introduction
The importance of aromatic amines is known, since aromatic
amines are commonly used in organic synthesis.1 Moreover,
aromatic amines are often used as effective targets in the
design and synthesis of drugs and bioactive molecules.2
Although there are numerous methods for the synthesis of
aromatic amines, ortho C(sp2)–H bond functionalization of
aromatic amines under transition metal catalysis has became a
powerful tool for the generation of diverse anilines.3 Various
metal catalysts such as Pd, Rh, Ir, Ru, etc have been used to
facilitate the C–H bond activation or functionalization of
aromatic amines. Recently, photoinduced C-H bond
functionalization of aromatic amines through radical process
has received continuous interests of chemists.4 Various
functional groups could be installed in the aromatic ring of
anilines under mild conditions via radical process. For example,
Willis and co-workers reported the sulfonylation of aniline
derivatives with sulfinate salts through a photoredox-catalyzed
reaction.4a Li and co-workers developed an intermolecular C−H
bond alkylation of aniline derivatives with α-bromo ketones
under visible-light catalysis.4b In the transformations, good
regioselectivity favoring the ortho-position of anilines was
observed
sulfonyl compounds.6-8 Among the approaches, C(sp2)–H bond
sulfonylation from sulfur dioxide has been developed by using
DABCO·(SO2)2 as the SO2 surrogate.8 For instance, Yang and co-
workers developed
a
copper-catalyzed C(sp2)–H bond
sulfonylation under base-free or ligand-free conditions starting
from heteroaryls, sulfur dioxide, and aryl halides, providing
diaryl sulfones in moderate to good yields.8a Direct C-H bond
sulfonylation of indoles with the insertion of sulfur dioxide was
achieved through a palladium-catalyzed reaction of 1-(pyridin-
2-yl)indoles,
DABCO·(SO2)2
and
aryldiazonium
tetrafluoroborates.8c Encouraged by these results, we
envisioned that the synthesis of sulfonated anilines via C–H
bond sulfonylation with the insertion of sulphur dioxide might
be feasible.
NR'2
NR'2
DABCO (SO2)2
R
+
R
Ar
Ar N2BF4
S
H
O
O
3
1
2
C-H bond sulfonylation of anilines
Scheme 1. A proposed route for the synthesis of sulfonated anilines
As part of a program in our laboratory for the synthesis of
sulfonyl compounds via insertion of sulfur dioxide,5 we are
interested in the sulfonylation of anilines from sulfur dioxide
via C–H bond sulfonylation
Since anilines could be easily oxidized to radical cation via a
single electron transfer (SET) under proper conditions,4 we
conceived that arylsulfonyl radical might be involved, thus
accomplishing the synthesis of sulfonated anilines via C–H
bond sulfonylation. In our previous report,5a we disclosed that
arylsulfonyl radical could be easily generated in situ from the
a.Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai 200438,
China. E-mail: jie_wu@fudan.edu.cn
b.School of Petrochemical Engineering, and Jiangsu Province Key Laboratory of Fine
Petrochemical Engineering, Changzhou University, Changzhou 213164, China
c.State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
China
combination
of
DABCO·(SO2)2
and
aryldiazonium
tetrafluoroborates. Therefore, the preparation of diverse
sulfonated anilines might be practicable from a three-
† Electronic Supplementary Information (ESI) available: [Experimental details and
spectral data, copies of 1H and 13C NMR spectra.]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1

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Page 2 of 4
ARTICLE
component reaction of anilines, sulfur dioxide, and
aryldiazonium tetrafluoroborates (Scheme 1). Thus, we started DABCO·(SO2)2 (0.2 mmol), p-methylphenyldiazonium tetrafluoroborate
to explore the feasibility of the C-H Bond sulfonylation of 2a (0.3 mmol), solvent (2.0 mL), N2, 8 h. b Isolated yield based on N,N-
anilines with the insertion of sulfur dioxide through a three- dimethyl-p-toluidine 1a. c In the presence of DABCO·(SO2)2 (0.3 mmol).
component reaction of anilines, DABCO·(SO2)2, and d N,N-Dimethyl-p-toluidine 1a was added dropwisely during 5 min.
aryldiazonium tetrafluoroborates.
Journal Name
a
Reaction conditions: N,N-dimethyl-p-toluidine 1aVie(w0.A2rticlme Omnolinl)e,
DOI: 10.1039/C8CC03465F
The scope generality for the C-H bond sulfonylation of
anilines with the insertion of sulfur dioxide was then explored.
A range of N,N-dimethyl anilines 1 reacted with DABCO·(SO2)2
Results and discussion
and aryldiazonium tetrafluoroborates
2 under the optimal
Initially, a model reaction of N,N-dimethyl-p-toluidine 1a,
DABCO·(SO2)2 and p-methylphenyldiazonium tetrafluoroborate 2a
was evaluated to optimize the reaction conditions. At the beginning,
the reaction was performed in THF at 50oC without any catalysts or
additives since the sulfonative reactions might occur under
catalyst- and additive-free conditions according to our
previous works.6 However, only a trace amount of product was
detected (Table 1, entry 1). A similar result was observed when
the solvent was changed to 1,4-dixoane, DMF, or DMSO (Table
1, entries 2-4). To our delight, the desired 2-sulfonylaniline 3a
was obtained in 36% yield when the reaction took place in
MeCN (Table 1, entry 5). A lower yield (22%) of product 3a was
generated (Table 1, entry 6) when the reaction occurred in 1,2-
dichloroethane (DCE). We further explored the reaction at
different temperatures. The result was inferior when the
reaction was performed at room temperature (Table 1, entry
7). Gratifyingly, the corresponding product 3a was formed in
49% yield when the reaction proceeded at 65 oC (Table1, entry
8). No better result was obtained when the reaction
temperature was changed to 80 oC (Table1, entry 9). A slightly
high yield was observed when the amount of DABCO·(SO2)2 was
increased (Table 1, entry 10). Interestingly, the corresponding
N,N,4-trimethyl-2-tosylaniline 3a was generated in 90% yield when
N,N-dimethyl-p-toluidine 1a was added to the reaction mixture
reaction conditions, leading to diverse 2-sulfonylanilines in
moderate to good yields. The results are shown in Table 2. This
three-component reaction was efficient under metal- and
additive-free conditions. It is noteworthy that different
functional groups including fluoro, chloro, bromo, methoxy,
Table 2. Scope exploration for the C-H bond sulfonylation of anilines
with the insertion of sulfur dioxide a
NMe2
H
NMe2
DABCO (SO2)2 MeCN
R
+
R
Ar
S
O
65 οC
Ar N2BF4
O
1
2
3
NMe2
p-Tol
NMe2
C6H4p-OMe
NMe2
C6H4p-Br
S
S
S
O
O
O
O
O
O
3a, 90% yield
3b, 58% yield
3c, 51% yield
NMe2
NMe2
NMe2
C6H4p-CF3
C6H5
C6H4o-CO2Me
S
S
S
O
O
O
O
O
O
3d, 63% yield
3e, 57% yield
3f, 56% yield
NMe2
NMe2
NMe2
dropwisely during 5 min (Table 1, entry 11)
.
C6H4p-F
C6H4o-Cl
C6H4p-CO2Et
S
S
S
O
O
O
O
O
O
Table 1. Initial studies for the reaction of N,N-dimethyl-p-toluidine 1a,
DABCO·(SO2)2 and p-methylphenyldiazonium tetrafluoroborate 2a. a
3g, 63% yield
3h, 87% yield
3i, 90% yield
NMe2
NMe2
NMe2
NMe2
p-Tol
NMe2
H
C6H4m-Cl
C6H4m-Me
C6H4p-Cl
DABCO (SO2)2 solvent
S
S
S
O
O
+
O
O
O
O
p-Tol N2BF4
temp
S
3j, 96% yield
3k, 62% yield
NMe2
3l, 82% yield
O
3a
O
2a
1a
NMe2
Entry
Temp (°C)
Solvent
THF
Yield (%)b
trace
trace
trace
trace
36
C6H4p-NO2
C6H4o,m-Me2
S
MeO
S
1
2
50
50
50
50
50
50
25
65
80
65
65
O
O
O
O
3n, 80% yield
3m, 48% yield
1,4-dioxane
DMF
NMe2
3
NMe2
4
DMSO
MeCN
DCE
C6H4m-Me
MeO
S
MeO
S
5
O
O
O
O
6
22
3o, 77% yield
3p, 90% yield
7
MeCN
MeCN
MeCN
MeCN
MeCN
trace
49
a Isolated yield based on N,N-dimethyl aniline 1.
8
9
44
10c
11c,d
53
trifluoromethyl, nitro, and ester were all compatible in this
transformation. For example, nitro-substituded product 3m could
be afforded in 48% yield, and the ester-containing product 3i was
90
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx

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Journal Name
ARTICLE
generated in 90% yield. For N,N-dimethyl anilines 1 with Table 2. As expected, the desired product 3a was not detected.
View Article Online
substitutions on the para-position, the C-H bond sulfonylation Furthermore, K2S2O5 as inorganic sulfiteDoOrI:t1h0e.10g3a9s/eCo8CuCs0s3u4l6fu5Fr
was exclusively occurred at the 2-position. In some cases, the dioxide was used as a replacement of DABCO.(SO2)2 in the
yields were moderate. Since the presence of copper catalyst reaction
of
N,N-dimethyl-p-toluidine
1a
with
p-
might assist the oxidative single electron transfer from radical methylphenyldiazonium tetrafluoroborate 2a. As a result, only
intermediate to cation intermediate, 10 mol % of CuCl or CuCl2 a trace amount of product 3a was observed. This evidence
was added in the reaction of N,N-dimethyl-p-toluidine 1a, indicated the important role of DABCO·(SO2)2 in the reaction
DABCO·(SO2)2 and p-methoxyphenyldiazonium tetrafluoroborate 2b. process.
However, no better result was obtained, and the
corresponding product 3b was obtained in 46% and 42% yields, results mentioned above,
respectively. proposed as shown in Scheme 3. We envisioned that
On the basis of previous reports4 and the experimental
plausible mechanism was
a
The substrate was further extended to N-methyl-p-toluidine aryldiazonium tetrafluoroborate would react with DABCO·(SO2)2,
1b and N-ethyl aniline 1c in the reaction of DABCO·(SO2)2 with p- giving rise to arylsulfonyl radical A and tertiary amine radical
methylphenyldiazonium tetrafluoroborate 2a (Scheme 2). cation. Tertiary amine radical cation would go through a single
Compound 3q was obtained in 35% yield as expected (Scheme electron transfer (SET) with aniline 1 to generate a radical
2, eq 1). The formation of a mixture of products 3r and 3r’ was cation B, with the release of DABCO (path a). Then radical
observed when N-ethyl aniline 1c was employed under the cation B would undergo tautomerization to produce radical
standard conditions (Scheme 2, eq 2). Anilines with electron- cation C, which would couple with arylsulfonyl radical A to
withdrawing groups were employed in the reactions as well. generate intermediate D. The subsequent deprotonation and
For instance, 4-fluoro-N,N-dimethyl aniline 1d reacted with aromatization would provide the desired sulfonated aniline 3.
DABCO·(SO2)2 and 3,5-dimethylphenyldiazonium tetrafluoroborate, Alternatively, arylsulfonyl radical A would attack aniline 1 to
giving rise to the desired product 3s in 23% yield (Scheme 2, eq 3). produce radical E (path b). Subsequently, tertiary amine radical
The corresponding products 3t and 3u were afforded in 29% and cation would be involved through a single electron transfer
25% yield respectively, when 4-fluoro-N-methyl aniline 1e or 4- (SET) leading to cation intermediate F. Followed by
chloro-N-methyl aniline 1f was used in the reaction of deprotonation would produce the final product 3.
DABCO·(SO2)2 with p-methylphenyldiazonium tetrafluoroborate 2a
O
O
(Scheme 2, eq 4).
NR'2
NR'2
S
- H+
NR'2
Ar
A
R
R
Ar
S
O
Ar
S
O
R
NHMe
p-Tol
NHMe
DABCO (SO2)2
MeCN
65 οC
O
O
C
3
D
+
(1)
p-Tol N2BF4
S
H
O
O
2a
1b
Ar N2BF4
DABCO
O
O
S
3q, 35% yield
NR'2
2
N
R
R
NHEt
DABCO
R'
R'
NHEt
Ts
DABCO (SO2)2
MeCN
65 οC
NHEt
B
R'
+
+
path a
path b
DABCO (SO2)2
O
p-Tol N2BF4
O
(2)
NR'2
NR'2
Ts
S
2a
Ar
3r'
3r
R
A
Ar
S
1c
O
1
O
3r/3r': 1/4, 57% yield
S
O
O
E
Ar
A
NMe2
NMe2
H
DABCO (SO2)2
MeCN
65 οC
DABCO
DABCO
(3)
+
Ar
Ar N2BF4
F
S
F
O
O
Ar: 3,5-Me2C6H3
1d
NR'2
NR'2
- H+
3s, 23% yield
R
R
Ar
S
O
Ar
S
NHMe
NHMe
H
DABCO (SO2)2
MeCN
65 οC
O
O
O
3
F
+
(4)
p-Tol
p-Tol N2BF4
X
S
X
Scheme 3. Plausible mechanism for the C-H bond sulfonylation of anilines
with the insertion of sulfur dioxide
O
O
2a
1e: X = F
1f: X = Cl
3t: X = F, 29% yield
3u: X = Cl, 25% yield
Conclusions
Scheme 2. Reactions of 4-methylphenyldiazonium tetrafluoroborate
2b, DABCO·(SO2)2, with other anilines.
In conclusion, we have described a C-H bond sulfonylation of
anilines with the insertion of sulfur dioxide under metal-free
conditions. 2-Sulfonylanilines are generated in moderate to
good yields through a three-component reaction of anilines,
DABCO·(SO2)2, and aryldiazonium tetrafluoroborates under
mild conditions. No metal catalyst or additives are needed in
this transformation. This direct C-H functionalization is highly
efficient, and broad functional group tolerance is observed. A
Subsequently, several control experiments were performed
to gain more insights into the reaction mechanism. The radical
scavenger of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)
(2.0 equiv) was added to the model reaction of N,N-dimethyl-
p-toluidine 1a, DABCO·(SO2)2 and p-methylphenyldiazonium
tetrafluoroborate 2a under the standard reaction shown in
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal Name
4
For selected examples, see: (a) T. C. Johnson, B. L. ElbVeiretw, AAr.tiJc.leFaOrnlleinye,
radical process is believed to be involved. In the reaction
process, arylsulfonyl radical and tertiary amine radical cation
generated in situ from DABCO·(SO2)2, and aryldiazonium
tetrafluoroborate are the key intermediates. Additionally,
tertiary amine radical cation acts as the electron carrier through
a single electron transfer process.
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Conflicts of interest
5
There are no conflicts to declare.
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Acknowledgements
Financial support from National Natural Science Foundation of
China (Nos. 21672037 and 21532001) and Jiangsu Province Key
Laboratory of Fine Petrochemical Engineering (KF1701) is
gratefully acknowledged.
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2
3
J. Lindley, Tetrahedron 1984, 40, 1433.
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