Photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and electron-deficient alkenes

Article abstract of DOI:10.1039/c9cc00347a

A photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and electron-deficient alkenes under mild conditions is achieved. This reaction proceeds through alkyl radicals formed in situ from alkyl iodides under visible light irradiation in the presence of a photoredox catalyst. The alkyl radical intermediates would react with sulfur dioxide leading to alkylsulfonyl radicals, which would be trapped by electron-deficient alkenes giving rise to alkyl sulfones. Various functional groups including nitro, halo, acetyl, sufonyl, and pyridinyl are all tolerated under the photoredox conditions.

Full text of DOI:10.1039/c9cc00347a

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DOI: 10.1039/C9CC00347A
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ARTICLE
Photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide,
and electron-deficient alkenes
Shengqing Ye,a Danqing Zheng,c Jie Wu*a,c and Guanyinsheng Qiu*b,c
Received 00th January 20xx,
Accepted 00th January 20xx
A photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and electron-deficient alkenes under mild conditions
is achieved. This reaction proceeds through alkyl radicals formed in situ from alkyl iodides under visible light irradiation in
the presence of photoredox catalyst. The alkyl radical intermediates would react with sulfur dioxide leading to
alkylsulfonyl radicals, which would be trapped by electron-deficient alkenes giving rise to alkyl sulfones. Various functional
groups including nitro, halo, acetyl, sufonyl, and pyridinyl are all tolerated under the photoredox conditions.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Transition metal-catalyzed coupling reactions of aryl/alkyl cheap. For instance, aryl/alkyl halides could react with sulfur
halides have been utilized broadly, due to the easily available dioxide and hydrazines under ultraviolet irradiation.8a
and cheap aryl/alkyl halides.1 Recently, reactions of aryl/alky Although this transformation was efficient, the reaction could
halides under photoredox catalysis have attracted much not be extended to other partners due to the ultraviolet
attention. It is well recognized that the photoinduced C-X bond irradiation. Thus, method development for the sulfonylation of
dissociation of aryl/alkyl halides would produce the aryl/alkyl halides with the insertion of sulfur dioxide under
corresponding carbon radicals via electron transfer.2 Therefore, mild conditions, especially in the presence of visible light,
the possibility for the
β-H elimination of alkyl halides under would be highly desirable. Herein, we report a photoredox-
transition metal catalysis may be avoided under photoinduced catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and
conditions. So far, the progress of photoinduced C-X bond electron-deficient alkenes under mild conditions. This reaction
dissociation has been witnessed. For example, Peters and Fu proceeds through alkyl radicals formed in situ from alkyl
reported the photoinduced Ullmann C–N coupling by using a iodides under visible light irradiation in the presence of
stoichiometric or a catalytic amount of copper salt under photoredox catalyst, leading to diverse sulfones. Various
visible light irradiation at room temperature.2a
functional groups including nitro, halo, acetyl, sufonyl, and
In the past decade, synthesis of sulfonyl compounds pyridinyl are all tolerated under the photoredox conditions.
through the insertion of sulfur dioxide has developed rapidly,3
O
O
SO2
which avoids the utilization of pre-installed sulfonyl
precursors.4 Currently, the sulfur dioxide surrogates including
DABCO·(SO2)2 (1,4-diazabicyclo[2.2.2]octane-sulfur dioxide)5-7
and inorganic sulfites8 have been used broadly in the
sulfonylation process. As part of a program for the generation
of sulfonyl compounds, we are interested in the radical
process with the insertion of sulfur dioxide.7 So far, various
radical precursors have been employed in the sulfonylation
reaction including aryldiazonium tetrafluoroborates,7 aryl/alkyl
PC (cat)
sulfones
S
Alkyl
I
Alkyl
Alkyl
hν
1
Scheme 1. Generation of sulfones under photoredox catalysis with the
insertion of sulfur dioxide
At the outset, a model reaction of cyclohexyl iodide 1a
,
DABCO·(SO2)2, and (E)-chalcone 2a in the presence of TTMS
and photocatalyst (5 mol %) was explored. The results are
summarized in Table 1. Initially, the reaction was catalyzed by
[Ir(dfCF3ppy)2(dtbbpy)]PF6 in 1,2-dichloroethane irradiated by
15 W blue LED (Table 1, entry 1). To our delight, the
corresponding sulfone 3a was obtained in 31% yield. Inferiors
results were observed when the solvent was changed to 1,2-
dioxane, MeCN, or MeOH (Table 1, entries 2-4). No reaction
occurred when the photocatalyst was replaced by Rhodamine
B (Table 1, entry 5). A slightly higher yield was afforded when
9-Mes-10-methyl acridinium perchlorate was used as the
photocatalyst (Table 1, entry 6). Several inorganic bases were
then screened (Table 1, entries 7-11), and it was found that the
transformation worked well when sodium acetate was used
halides,9
diaryliodonium
salts,10
and
potassium
alkyltrifluoroborates.11 Among these precursors, aryl/alkyl
halides are especially attractive, which are easily available and
a.Institute for Advanced Studies, Taizhou University, 1139 Shifu Avenue, Taizhou
318000, China. E-mail: jie_wu@fudan.edu.cn
b.College of Biological, Chemical Science and Engineering, Jiaxing University, 118
Jiahang Road, Jiaxing 314001, China. E-mail: qiuguanyinsheng@mail.zjxu.edu.cn
c.Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai 200438,
China.
S. Ye and D. Zheng contribute equally
† 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

ChemComm
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Journal Name
leading to the expected product 3a in 42% yield (Table 1, entry
The generality of reaction scope was thenViienwvAertsictliegOantleinde
DOI: 10.1039/C9CC00347A
11). Since the presence of halide would promote the under the above optimized conditions. The result is shown in
conversion, thus the reaction was examined with the addition Scheme 2. It was found that this transformation with a range
of sodium bromide or sodium iodide (Table 1, entries 12-13). of alkyl iodides was efficient, which proceeded smoothly giving
Gratifyingly, the reaction with the addition of sodium iodide rise to the corresponding sulfones
provided the desired product 3a in 66% isolated yield (Table 1, iodotetrahydro-2H-pyran but also 3-iodooxetane was suitable
entry 13). Further exploration revealed that the yield was substrate in the reaction of DABCO·(SO2)2 and (E)-chalcone 2a
3 as expected. Not only 4-
,
enhanced to 71% when iodine was employed instead (Table 1, leading to the desired product 3b and 3e, respectively. It was
entry 14). No change was observed when the amount of base noteworthy that only alkyl iodide was effective in this
was increased (Table 1, entry 15). The yield could not be transformation, and alkyl chloride was inert under the
improved by changing the amount of TTMS (Table 1, entry 16). conditions. For example, compound 3g was produced in 66%
No reaction occurred in the absence of photocatalyst (Table 1, yield, and the chloro group was remained. Reaction of ester-
entry 17). Only a trace amount of product was obtained when containing substrate also worked well, affording the desired
the reaction was performed in the dark (Table 1, entry 18).
product 3h in 58% yield. Other substituted chalcones were
examined subsequently, and various functional groups
including methoxy, nitro, and chloro were all tolerated.
Further exploration revealed cyclohexyl iodide 1a reacted with
DABCO·(SO2)2 and 4-vinylpyridine giving rise to the
corresponding product 3t in 72% yield. Compound 3u was
generated in 46% yield when (vinylsulfonyl)benzene was
employed as the substrate. However, the reactions failed to
produce the corresponding products when other acrylates,
Table 1. Initial studies for the reaction of cyclohexyl iodide 1a
DABCO·(SO2)2, and (E)-chalcone 2a a
,
I
1a
photocatalyst (5 mol %)
(TMS)3SiH, additive
O
O
O
S
Ph
+
Ph
Cy
Ph
base, solvent
15 W blue LED
DABCO (SO2)2
2a
Ph
O
3a
-
F3C
PF6
F
styrenes or Michael acceptor systems holding a
substituent were used as substrates.
β-alkyl
tBu
N
Ir
CO2H
Cl-
N
N
F
F
N
tBu
Alkyl
DABCO (SO2)2
I
Mes-Acr+ (5 mol %)
O
O
1
N
EWG
S
+
Et2N
O
NEt2
F
R
Alkyl
EWG
ClO4
(TMS)3SiH, NaOAc, I2
DCE, 15 W blue LED
F3C
2
R
[Mes-Acr+]ClO4
-
3
[Ir(dfCF3ppy)2(dtbbpy)]PF6
Rhodamine B
O
O
O
O
O
O
O
O
S
Ph
S
Ph
S
Ph
S
Ph
Ph
Entry
PC
[Ir]c
Additive
Base
-
Solvent Yield (%)b
Cy
Me
Ph
3a, 71%
O
O
Ph
O
Ph
O
Ph
O
O
1
2
-
DCE
dioxane
MeOH
MeCN
DCE
31
23
trace
18
0
3d, 40%
[Ir]c
-
-
3b, 47%
3c, 70%
3
[Ir]c
[Ir]c
-
-
O
O
O
O
S
O
O
S
O
O
S
S
Ph
Ph Cl
Ph
tBu
( )
( )
5
3
4
-
-
O
Ph
O
Ph
O
Ph
O
Ph
O
3h, 58%
EtO
5
Rhodamine B
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
Mes-Acr+
-
-
-
3e, 60%
3f, 70%
3g, 66%
6
-
-
DCE
35
22
24
37
42
35
44
66
71
72
63
0
O
O
O
O
O
O
O
O
7
-
K2CO3
Na2CO3
NaHCO3
NaOAc
Na2HPO4
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
DCE
S
Ph
S
Ph
S
Ph
S
p-Tol
nBu
iPr
( )
Cy
5
8
-
DCE
Ph
O
Ph
O
Ph
O
Ph
O
9
-
DCE
3i, 58%
3j, 72%
3k, 70%
3l, 68%
10
11
12
13
14
15d
16e
17f
18g
-
-
DCE
O
O
O
O
S
O
O
S
C6H4p-Br
C6H4p-OH
S
C6H4p-OMe
DCE
Cy
Cy
Cy
NaBr
NaI
I2
DCE
Ph
O
Ph
O
Ph
O
DCE
3o, 56%
3m, 66%
3n, 68%
DCE
O
O
O
O
O
O
O
O
S
Ph
S
Ph
S
Ph
S
Ph
O
Cy
p-ClC6H4
3r, 54%
Cy
m-ClC6H4
3s, 47%
I2
DCE
Cy
p-MeOC6H4
Cy
p-NO2C6H4
O
O
O
I2
DCE
3p, 57%
3q, 38%
I2
DCE
Mes-Acr+
I2
DCE
trace
O
O
O
O
S
Ph
S
Cy
S
a
Cy
O
O
Reaction conditions: Chalcone 1a (0.2 mmol), iodocyclohexane 2a
O
O
N
S
Ph
N
( )
(2.0 equiv. 0.4 mmol), DABSO (0.8 equiv.), TTMS (1.0 equiv, 0.2mmol),
additives (10 mol %), base (1.5 equiv. 0.3 mmol), photocatalyst (5
mol %), solvent (3.0 mL), N2, rt, under blue LED irradiation (15W) for
4
3u, 46%
3t, 72%
Ph
O
3v, 66%
O
O
S
Me
Cy
b
c
d
48h. Isolated yield based on 1a
.
[Ir(dfCF3ppy)2(dtbbpy)]PF6. In the
Ph
O
presence of base (2.0 equiv. 0.4 mmol). e In the presence of TTMS (1.2
equiv. 0.24 mmol). f In the absence of photocatalyst. g In the dark.
3w, 55%
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx

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Journal Name
Mes-Acr+*
Mes-Acr
Scheme 2. Scope investigation for the photoredox-catalyzed
sulfonylation of alkyl iodides , sulfur dioxide, and electron-deficient
alkenes
hν
View Article Online
DOI: 10.1039/C9CC00347A
(TMS)3SiH
1
I
Mes-Acr+
HI
2
I
Alkyl
1
(TMS)3Si
a
As mentioned above, we proposed that under photoredox
catalysis, alkyl radical intermediates would be produced to
initiate the reaction. Therefore, several control experiments
were performed, as presented in Scheme 3. As expected, no
reaction occurred with the addition of 2,2,6,6-tetramethyl-1-
O
O
I
S
S
Alkyl
EWG
O
O
(TMS)3Si
I
R
B
S
Alkyl
EWG
A
H+
O
O
SO2
R
S
Alkyl
Alkyl
b
piperidinyloxy (TEMPO) in the mixture of cyclohexyl iodide 1a
DABCO·(SO2)2, and (E)-chalcone 2a under the standard
conditions, and compound was detected by HRMS (Scheme 3,
,
EWG
O
O
(TMS)3SiH
EWG
R
Alkyl
4
(TMS)3Si
2
3
R
eqn a). Additionally, (iodomethyl)cyclopropane was employed
in the reaction of DABCO·(SO2)2 with (E)-chalcone 2a, resulting
in the formation of compound 3x in 56% yield (Scheme 3, eqn
b). This result demonstrated that cyclopropylmethyl radical
might be generated during the reaction process. These results
indicated that a radical process might be involved, as proposed
in Scheme 4.
Scheme 4. Plausible mechanism
In summary, we have described a photoredox-catalyzed
sulfonylation of alkyl iodides, sulfur dioxide, and electron-
deficient alkenes under mild conditions. This reaction proceeds
through alkyl radicals formed in situ from alkyl iodides under
visible light irradiation in the presence of photoredox catalyst.
The alkyl radical intermediates would react with sulfur dioxide
leading to alkylsulfonyl radicals, which would be trapped by
electron-deficient alkenes giving rise to alkyl sulfones. Various
functional groups including nitro, halo, acetyl, sufonyl, and
pyridinyl are all tolerated under the photoredox conditions.
I
1a
TEMPO
O
Mes-Acr+ (5 mol %)
3a
(n.d.)
+
(a)
+
N
Cy
Ph
Ph
(TMS)3SiH, NaOAc, I2
DCE, 15 W blue LED
O
DABCO (SO2)2
2a
4
detected by HRMS
O
O
O
Mes-Acr+ (5 mol %)
S
Ph
I
+
(b)
Ph
Ph
(TMS)3SiH, NaOAc, I2
DCE, 15 W blue LED
Ph
3x, 56%
O
DABCO (SO2)2
2a
Conflicts of interest
Scheme 3. Control experiments
On the basis of above results and previous reports,11 we
postulated that under visible light irradiation, the excited state
of photocatalyst would assist the formation of
trimethylsilylsilyl radical (Scheme 4). Thus, trimethylsilylsilyl
There are no conflicts to declare.
Acknowledgements
Financial support from National Natural Science Foundation of
China (Nos. 21672037 and 21532001) is gratefully
acknowledged.
radical would react with alkyl iodide
intermediate, which would be captured by sulfur dioxide to
provide alkylsulfonyl radical. Then, alkylsulfonyl radical would
1 leading to alkyl radical
attack the double bond of electron-deficient alkene
rise to radical intermediate . Subsequently, two possible
pathways might occur. In path a, radical intermediate would
undergo a reductive single electron transfer (SET) to produce
anion intermediate . Further protonation would afford the
corresponding sulfone . Alternatively, radical would go
through proton abstraction from TTMS, giving rise to the
desired product (path b).
2, giving
A
Notes and references
A
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3
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3
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Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC00347A
Photoredox-catalyzed sulfonylation of alkyl iodides, sulfur
dioxide, and electron-deficient alkenes
Shengqing Ye, Danqing Zheng, Jie Wu,* and Guanyinsheng Qiu *
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
Graphical Abstract
O
O
Alkyl
I
Mes-Acr+ (5 mol %)
EWG
S
+
R
I
Alkyl
EWG
(TMS)3SiH, NaOAc, I2
DCE, 15 W blue LED
DABCO (SO2)2
R
O
O
SO2
PC (cat)
h
S
Alkyl
Alkyl
Alkyl
A photoredox-catalyzed sulfonylation of alkyl iodides, sulfur dioxide, and electron-deficient alkenes under mild conditions is
achieved. Various functional groups including nitro, halo, acetyl, sufonyl, and pyridinyl are all tolerated under the photoredox
conditions.