Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis

Article abstract of DOI:10.1021/acs.orglett.1c01050

An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful organosulfones.

Full text of DOI:10.1021/acs.orglett.1c01050

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Letter
Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis
Qiuli Yan, Wenwen Cui, Xiuyan Song, Guiyun Xu, Min Jiang, Kai Sun, Jian Lv, and Daoshan Yang*
Cite This: Org. Lett. 2021, 23, 3663−3668
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ABSTRACT: An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our
protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were
obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful
organosulfones.
rganosulfones, one of the most valuable sulfur-
containing molecules, are pivotal structural motifs
limit their wide applications, which thus stimulates chemists to
search for more efficient and practical processes.
O
found in several biologically active molecules and argochem-
Recently, tremendous progress has been made in the field of
photocatalytic organic transformations since it provides a green
and sustainable means for building carbon−heteroatom and
carbon−carbon bonds.8 In this respect, diverse and efficient
photocatalysts, including transition metal complexes based on
iridium(III) and ruhenium(II), and organic dyes, have been
extensively developed.9 Nevertheless, most of these photo-
catalysts still have some drawbacks, such as potential toxicity,
high cost, the scarity of the metal salts, and lower photo-
stability, which might impede their wide applications. There-
fore, copper complexes are gaining more attention for visible-
light-promoted transformations. Copper complexes, especially
copper-phenanthroline derivatives, usually have long excited
state lifetimes and strong photoexcited reducing ability and
also tend to undergo structural redistribution and ligand
exchange which provide unique reaction pathways.10 In
addition to being an economically attractive alternative to
iridium or ruthenium photocatalysts, CuI complexes also have
a special role in facilitating electron transfer to organic
substrates. In 2012, Hwang et al. initially developed an
efficient CuCl-catalyzed, visible-light-induced Sonogashira
cross-coupling reaction under mild conditions (Scheme
icals (Figure 1).1 Additionally, sulfones are also versatile
Figure 1. Examples of organosulfones in biologically active molecules.
chemical building blocks widely utilized in synthetic
chemistry.2 Therefore, the development of efficient and
sustainable approaches toward the construction of organo-
sulfones is highly desirable. Conventionally, there are five
methods for the synthesis of these valuable molecules: (a)
oxidation of sulfoxide or ssulfides;3 (b) cross-coupling
reactions of sulfinate salts with aryl haildes under transition-
metal-catalyzed conditions;4 (c) difunctionalization of alkynes
and alkenes with sulfinate salts or sulfinic acids;5 (d) sulfur
dioxide fixation with a SO2 surrogate;6 (e) sulfonyaltion of
arenes via a Friedel−Crafts-type pathway.7 These methods are
successful; however, the use of foul-smelling sulfides or
sulfoxides, strong oxidants, and harsh reation conditions can
Received: March 27, 2021
Published: April 21, 2021
https://doi.org/10.1021/acs.orglett.1c01050
© 2021 American Chemical Society
Org. Lett. 2021, 23, 3663−3668
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Letter
1a).11 Since the pioneering work by the Hwang group, visible-
light-promoted copper catalyst systems have been extensively
Initially, we selected 4-bromoacetophenone (1a) and
sodium 4-methylbenzenesulfinate (2a) as the coupling partners
to explore the optimized reaction conditions (Table 1).
Scheme 1. Strategies for the Copper-Catalyzed Coupling
Reactions under Visible-Light Conditions
a
Table 1. Optimization of Reaction Conditions
b
entry
catalyst
ligand
base
yield (%)
1
2
3
4
5
6
7
8
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
none
A
B
C
D
E
F
G
H
I
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
none
30
20
31
n.r.
42
37
44
trace
63
54
57
43
37
77
n.r.
90
n.r.
9
10
11
12
13
14
15
16
17
J
studied. In the past few years, a large number of copper(I)
complexes have been studied as visible light catalysts.12 For
instance, Fu’s group demonstrated a green and efficient visible-
light-induced enantioselective C−N cross-coupling using a
copper complex as the precursor of the photocatalyst (Scheme
1b).13 In 2018, Lalic and co-workers reported a mild copper-
catalyzed visible-light-promoted alkylation of terminal alkynes
with alkyl iodides (Scheme 1c).14 Very recently, Zhang et al.
described an efficient visible-light-induced, copper-catalyzed
asymmetric alkylation of azoles (Scheme 1d).15 The key step
in the transformations mentioned above is the photoexcitation
of the copper−nucleophile complex (LCuNu*) followed by
electron transfer to an alkyl halide. It still remains a formidable
challenge to establish different catalytic models for diverse
organic transformations by using copper complexes as
photocatalysts under visible light irradiation.
On the other hand, although great progress has been made
in the area of visible-light-promoted C−S bond forming
reactions, only limited examples of arylation of sulfinate salts
under visible-light irradiation have been sporadically re-
ported.16 Additionally, ultraviolet (UV) light-induced coupling
of sulfinates with aryl halides was reported.17 However, these
developed methods could possess some limitations, including
the use of expensive and toxic Ir/Ru organometallic complexes,
bases, and high-energy UV irradiation. Therefore, there is still
ample room for innovation, and the development of alternative
visible-light promoted strategies for the construction of
organosulfones as supplements to the existing methods still
remains very attractive. As a part of our continuing interest in
photochemical transformations,18 we herein disclose a visible-
light-promoted method for the synthesis of organosulfones
from aryl halides and sulfinate salts using [(BINAP)Cu-
(NCMe)]PF6] generated in situ as the photocatalyst under
mild conditions (Scheme 1d).
D and I
D and H
E and H
I
none
I
I
none
none
none
c
Cu(CH3CN)4PF6
Cu(CH3CN)4PF6
d
a
Reaction condions: 1a (0.3 mmol), 2a (0.45 mmol), [Cu-
(CH3CN)4PF6] (10 mol %), ligand (15 mol %), Cs2CO3 (0.6
mmol) and degassed DMSO (2 mL) at room temperature under
b
irradiation with 20 W blue LED (455 nm) for 16 h. The yields were
c
determined by 1H NMR with CH2Br2 as an internal standard. 1a/2a
d
= 1:3. No light.
Delightedly, a 30% yield of cross-coupling product 3a was
obtained in the presence of 10 mol % Cu(CH3CN)4PF6, 15
mol % 2,2′-dipyridyl (A), and Cs2CO3 in DMSO at room
temperature for 16 h under an irradiation of visible light with a
20 W blue LED (455 nm). Next, other ligands, bases, and
solvents were also investigated (see Table S1 in the Supporting
Information (SI) for the details). According to the results from
optimization of the reaction conditions, we determined that
Cu(CH3CN)4PF6 as the catalyst, BINAP as the ligand, and
DMSO as the solvent are suitable in the present photocatalytic
sulfonylation pathway.
After obtaining the optimized conditions, the substrate
scope of this sulfonylation transformation was explored
(Scheme 2). To our delight, diverse aryl halides smoothly
reacted with various sulfinates, delivering the desired organo-
sulfones in moderate to good yields. For this photocatalytic
system, the aryl iodides possessing electron-withdrawing
functional groups generally have higher reactivity, while
those bearing electron-donating ones generally have lower
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Letter
a b
,
Scheme 2. Substrate Scope of Aryl halides with Sulfinates
Scheme 3. Synthetic Applications
to the desired sulfonylated products 3ap and 3aq in moderate
yields.
In order to verify the role of the CuI-based photocatalyst, the
copper complex (6) was synthesized according to the previous
literature.19 Then, this copper catalyst (6) was then applied in
place of the combination of Cu(MeCN)4PF6 and BINAP as
the photocatalyst for the sulfonylation transformation. To our
delight, the desired product (3a) was obtained in almost the
same yield as that under the standard conditions (Scheme 4).
Scheme 4. Control Experiments
a
Reaction condions: 1 (0.2 mmol), 2 (0.6 mmol), [Cu-
(CH3CN)4PF6] (10 mol %), BINAP (15 mol %), and degassed
DMSO (2 mL) at room temperature under irradiation with 20 W blue
b
c
LED (455 nm) for 16 h. Isolated yield. At 60 °C.
reactivity (3g−3i). In addition, the investigated compounds
did not have an obvious steric effect; aryl halides bearing
formyl or cyano groups at different positions reacted with
sulfinates to afford the desired products (3f, 3g, 3q, and 3v)
smoothly. Other heteroaryl halides such as 2-bromopyrimidine
and 3-iodoquinoline were tested. Satisfactorily, these substrates
also gave sulfonylated products 3w, 3ac, and 3ah in 46−90%
yield. Notably, heteroaryl sulfinates including sodium pyridine-
3-sulfinate and sodium thiophene-2-sulfinate were also
examined, which delivered the cross-coupling products (3x,
3y, 3z, 3aa, 3af, and 3ag) in moderate yields. It should be
noted that the aryl sulfinates show higher reactivity than the
alkyl ones (3an and 3ao). In addition, vinyl bromides could
also be applied in our developed photocatalytic conditions (3aj
and 3ak). Furthermore, other nucleophiles including 4-
methylbenzenethiol, p-tolylmethanamine, p-cresol, p-tolylme-
thanol, and p-toluidine were also tested under the standard
conditions. Unfortunately, no desired products were observed
(see the SI for details). Diverse functional groups such as
aldehyde, methoxy, cyano, methyl, and ester were compatible
in the visible-light conditions.
However, treatment of the copper complex (6) with sodium 4-
methylbenzenesulfinate (2a) did not afford the LCuNu
complex (7) (see the SI for detail). These preliminary
experimental results showed that this CuI photocatalyst
generated in situ was the active photocatalyst in the present
transformation.
To further illuminate the photoreactivity of the CuI
photocatalyst, we measured the UV/vis absorptions of the in
situ formed [(BINAP)Cu(NCMe)]PF6], as well as other
components in the reaction system, such as 1a, 2a, Cu-
(CH3CN)4PF6, BINAP, and their combination (Figure 2a; see
the SI for details), respectively. [(BINAP)Cu(NCMe)]PF6]
and the in situ generated [Cu(CH3CN)4PF6 + BINAP]
showed almost the same absorption circumstances which
extended into the visible region. For 1a, 2a, Cu(CH3CN)4PF6,
and BINAP, the absorptions all had wavelengths of <300 nm.
To further understand the redox states of the CuI
photocatalyst that might be involved in this photocatalytic
sulfonylation process, mechanistic studies by EPR spectrosco-
py were performed. When 5,5-dimethyl-1-pyrroline N-oxide
(DMPO), a well-known free radical spin-trapping agent, was
added to the solution of Cu(CH3CN)4PF6, BINAP, and 1a,
A gram-scale synthesis of 3a using 4-bromoacetophenone
(1a) and sodium 4-methylbenzenesulfinate (2a) was per-
formed (Scheme 3a). Under the standard conditions, the
desired product 3a was constructed in 81% yield (5.0 mmol
scale). In addition, this protocol could be applied to the
postmodification of biologically related molecules. As shown in
Scheme 3b, an L-menthol derivative 1h could be transformed
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Letter
Scheme 5. Possible Reaction Mechanism
Figure 2. (a) Fluorescence quenching experiments. (b) EPR spectra
of the DMPO-radical adduct.
obvious carbon-centered radical signals was observed (g =
2.004, AN = 1.46 mT, AH = 2.24 mT) under irradiation with
20 W blue LED (455 nm) for 5 min (Figure 2b, red line).
Notably, no sulfonyl radical signal was observed in the present
transformation. To our delight, a Cu(II) signal (g∥ = 2.22, g⊥ =
2.03) was also detected under irradiation with 20 W blue LED
(455 nm) for 20 min (see Figure S16, SI). However, no radical
signal was observed without light irradiation (Figure 2b, black
line). These results preliminarily support the SET process
between CuI complex and 1a.
To investigate the mechanism further, Stern−Volmer
fluorescence quenching experiments were carried out. The
fluorescence intensity of the excited state of the in situ formed
[(BINAP)Cu(NCMe)]PF6] was significantly reduced when
the solution of 1a was added (Figure 3a). Moreover, Figure 3b
in situ generated CuI complex [(BINAP)Cu(NCMe)]PF6] was
excited by visible light irradiation leading to the excited species
CuL*. Next, an SET process from the excited species CuL* to
aryl halides afforded the radical anion I and LCuII species.
Fragmentation of Ar−X•− (I) gave the aryl radical II, which
subsequently reacted with the CuII complex to produce Ar−
CuIII intermidate III. Then, the intermidate III reacted with
sulfinates through a ligand exchange process to furnish
intermidate IV. Finally, reductive elimination of IV would
afford the sulfones 3 and regenerated the catalytic species
LCuI.
In conclusion, we have successfully disclosed an elegant
visible-light-promoted, copper-catalyzed sulfonylation of aryl
halides with sulfinates. This method has demonstrated mild
conditions and a broad substrate scope. A series of organo-
sulfones can be effectively obtained in moderate to good yields
with good functional group tolerance. In addition, satisfactory
results were also obtained in gram scale experiments. We
anticipate that the current strategy can provide more insights
to design a copper complex for visible-light promoted organic
transformations. Further studies to determine the mechanistic
details of this process and to expand the applications of this
synthetic strategy are ongoing in our laboratory.
Figure 3. Fluorescence quenching experiments.
showed an obvious linear relationship between the concen-
trations of 1a and the fluorescence intensities. However,
further experiments indicated that 4-methylbenzenesulfinate
(2a) did not quench the fluorescence of the [(BINAP)Cu-
(NCMe)]PF6] (see the SI for details). These preliminary
results indicated that the excited state of the CuI complex was
quenched by the substrate 1a. The excited redox potential of
CuI complex [(BINAP)Cu(NCMe)]PF6] (−3.04 V vs Ag/
AgCl) and the reductive potential of 1a (−2.00 V vs Ag/AgCl)
suggested that a single electron transfer (SET) event was
presumably engaged in the present reaction. In addition, we
envisioned that sodium sulfinate 2 (TsNa, Eox = +1.0 V vs Ag/
AgCl in CH3CN) could not react with CuIIL ([(BINAP)Cu-
(CH3CN)]PF6], E1/2 = 0.14 V vs Ag/AgCl in CH3CN) to give
a sulfonyl radical through an SET pathway in the present
system.20 An on/off experiment showed that continuous
irradiation with blue light is necessary (Figure S14).
Furthermore, the apparent quantum efficiency (455 nm)
values (AQE) for the model reaction was calculated to be
0.14% showing that a radical-chain process might not be
involved (see the SI for details).
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c01050.
General experimental procedures, mechanistic experi-
ments, and compound characterization data, including
the 1H/13C NMR spectra, and HRMS date spectra
(PDF)
AUTHOR INFORMATION
■
Corresponding Author
Daoshan Yang − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China;
orcid.org/0000-0002-3047-5416; Email: yangdaoshan@
tsinghua.org.cn
Based on these preliminary experimental results above, a
plausible reaction pathway is proposed in Scheme 5. First, the
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Organic Letters
Authors
pubs.acs.org/OrgLett
Letter
Photocatalysis. Angew. Chem., Int. Ed. 2019, 58, 13499. (c) Liu, K.-
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(b) Hernandez-Perez, A. C.; Collins, S. K. Heteroleptic Cu-Based
Sensitizers in Photoredox Catalysis. Acc. Chem. Res. 2016, 49, 1557.
Qiuli Yan − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China
Wenwen Cui − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China
Xiuyan Song − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China
Guiyun Xu − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China
Min Jiang − College of Materials, Chemistry and Chemical
Engineering, Hangzhou Normal University, Hangzhou
310036, P. R. China
Kai Sun − College of Chemistry and Chemical Engineering,
YanTai University, Yantai 264005, P. R. China;
orcid.org/0000-0002-0041-6044
Jian Lv − Key Laboratory of Optic-electric Sensing and
Analytical Chemistry for Life Science, MOE, College of
Chemistry and Molecular Engineering, Qingdao University of
Science and Technology, Qingdao 266042, P. R. China;
orcid.org/0000-0001-7641-5411
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01050
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Natural Science Foundation
of of Shandong Province (ZR2020JQ07, ZR2016JL012), the
National Natural Science Foundation of China (21302110,
21801007), The Taishan Scholars Construction Projects
(tsqn201812075), Youth Innovation Science and Technology
Plan of Colleges and University in Shandong Province
(2019KJC003), and the Scientific Research Foundation of
Qingdao University of Science and Technology.
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Org. Lett. 2021, 23, 3663−3668