Rongalite as a sulfone source: A novel copper-catalyzed sulfur dioxide anion incorporation process

Article abstract of DOI:10.1039/d0cc05800a

A novel copper-catalyzed sulfur dioxide anion incorporation cascade for the synthesis of 1-thiaflavanone sulfones has been disclosed using rongalite as an economic and safe sulfone source. A series of 1-thiaflavanone sulfones were synthesized from easily prepared 2′-iodochalcone derivatives in excellent yields. This transformation proceeds through consecutive formation of two C-S bonds, which is the first example of SO22- being used to construct sulfone motifs under copper-catalyzed conditions.

Full text of DOI:10.1039/d0cc05800a

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Chen, B. Tang,
C. He, J. Ma, S. Zhuang, Y. Wu and A. Wu, Chem. Commun., 2020, DOI: 10.1039/D0CC05800A.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC05800A
Journal Name
COMMUNICATION
Rongalite as Sulfone Source: A Novel Copper-Catalyzed Sulfur
Dioxide Anion Incorporation Process
Xiang-Long Chen, Bo-Cheng Tang, Cai He, Jin-Tian Ma, Shi-Yi Zhuang, Yan-Dong Wu* and An-Xin
Wu*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Rongalite (HOCH2SO2Na·2H2O) is an inexpensive and abundant
industrial product that has been extensively used in the rubber, dye,
and veterinary industries.13 Furthermore, rongalite can also serve as
A novel copper-catalyzed sulfur dioxide anion incorporation
cascade for the synthesis of 1-thiaflavanone sulfones has been
disclosed using rongalite as an economic and safe sulfone source. A
series of 1-thiaflavanone sulfones were synthesized from easily
prepared 2’-iodochalcone derivatives in excellent yields. This
transformation proceeds through consecutive formation of two C-
S bonds, which is the first example of SO22- being used to construct
sulfone motifs under copper-catalyzed conditions.
2-
a SO2 equivalent14 in some sulfonylation processes. However,
reaction models for sulfur dioxide anion are limited to nucleophilic
attack14a,15 and some radical processes,16 therefore broadening the
applications of rongalite are of great necessary. Unlike the neutral
sulfur dioxide molecule, the insertion of sulfur dioxide anion into a
carbon-metal bond is more difficult because it is negatively charged.
We noticed that the rongalite seemed to serve as a masked sulfinate
(or sulfinate with a leaving group). So we envisaged that replacing C-
[M] bond insertion with Ullmann-type C-S bond coupling might be
feasible, and producing sulfinate as an intermediate, followed by
intramolecular cyclization. Herein, we disclose a novel process to
Sulfone cores are extensively applied in bioactive and
agrochemical molecules.1 Among them, cyclic sulfonyl units have
drawn much attention, owing to their unique pharmacological2 and
photoelectric3 properties. In the last few decades, much research
effort has been focused on the efficient assembly of cyclic sulfones,
including radical-induced bicyclization cascades for polycyclic
sulfones,4 SO2/I exchange of cyclic diaryliodonium salts,5 ring-closing
metathesis of linear sulfones,6 cyclization of alkynyl(aryl)iodonium
salts with alkyl sulfinates,7 Smiles rearrangement–sulfinate addition
sequences to construct cyclic sulfones,8 and other methods.9
Specially, concise synthesis methods and new sulfone source has
attracted the synthetic chemists’ attention for the construction of
cyclic sulfones. In 2016, Wu and co-workers reported an elegant one-
step method for the synthesis of benzo[b]thiophene 1,1-dioxide
derivatives via SO2 insertion into a C-Cu bond using DABSO (a 1,4-
diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct) as the sulfone
source (Scheme 1a).10 Furthermore, cyclic sulfone products can also
be derived from cyclic sulfur substrates.11 For example, Sekar and co-
2-
incorporate SO2 into 2’-iodochalcones for the construction of 1-
thiaflavanone sulfones using rongalite as a sulfone source (Scheme
1c).
(a) Wu's work
O
SO2
O
B(OH)2
S
R1
[Cu]
R1
R2
+
DABCO (SO2)2
R2
(b) Sekar's work
O
S
O
S
O
Further
oxidization
S
R
R
[Cu]
+
R'
KS
OEt
R'
O
O
I, Br
R'= aryl
only one example
Two steps synthesis of 1-thiaflavanone sulfone
(c) This work
2-
SO2
O
workers reported
a domino process for the synthesis of
O
R1
R1
[Cu]
thioflavanones, which can be further oxidized to 1-thiaflavanone
sulfones (Scheme 1b).12 Despite this progress, economical sulfone
sources and novel methods for the construction of cyclic sulfones
remain in high demand.
O
S
+
R'
HO
S
R'
ONa 2H2O
O
O
I
R'= aryl, alkyl
36 examples
Rongalite(~0.03$/g)
industrial product
One step synthesis of 1-thiaflavanone sulfones
Scheme 1. Previous works and present sulfonylation process.
This investigation was initiated by the treatment of 2’-
o
iodochalcone (1a) with rongalite (2) in a 1:2 ratio at 110 C in the
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of
Chemistry, Central China Normal University, Wuhan 430079, P. R. China. E-mail:
chwuyd@mail.ccnu.edu.cn.
presence of Cu(OAc)2 (20 mol %), using DMF as solvent. To our
delight, 1-thiaflavanone sulfone (3a) was isolated in 11% yield (Table
1, entry 1). Subsequently, we examined the reaction in different
solvents, with CH3CN giving the best result (entries 2-5). Furthermore,
a series of phenanthroline-type ligands and bi/terpyridine ligands
were screened to further improve the yield of 3a (see Supporting
chwuax@mail.ccnu.edu.cn.
†Electronic Supplementary Information (ESI) available: Experimental details,
characterization of compounds, copies of 1H and 13C spectra for selected
compounds, and CIF files of 3a. CCDC 1973077. For ESI and crystallographic data in
CIF or other electronic format see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
Information). Pleasingly, 1,10-phenanthroline was found to be the yields. 4-Trifluoromethoxy-substituted 2’-iodochalcone was also
optimal ligand, affording 3a in 42% yield (entry 6). Owing to the poor tolerated, with corresponding product 3nDoObI:ta10in.1e0d39Vii/neDw08AC1rtC%ic0le5yO8in0el0lindAe.
solubility of rongalite in CH3CN, we decided to screen phase-transfer Next, substrates bearing fluoro, chloro, and bromo substituents,
catalysts in the reaction. Accordingly, adding tetrabutyl-ammonium which allowed potential further functionalization, were found to be
salts (1 equiv.) had a positive effect on the reaction (entries 7-10). tolerated in this sulfonylation reaction (3o-3s). Furthermore, strong
Among them, Bu4NCl showed the best reactivity, giving an increased electron-withdrawing groups resulted in moderate to good yields
yield of 67% (entry 8). Further screening of copper salts indicated (3t-3v). To our delight, amine- and sulfur-containing products were
that Cu(OTf)2 was the best choice, which further improved the yield isolated in notable yields (3w and 3x). Additionally, naphthalene and
to 76% (entries 11-15). Decreasing the dosage of rongalite inhibited heteroaryl groups were compatible with this transformation (3y-
the reaction (entry 16), while increasing the rongalite dosage to 3 3ab). Substrate bearing a conjugated moiety was also converted into
equiv. slightly enhanced the yield (entry 17). Further increasing the corresponding product 3ac in 77% yield. Finally, 2’-iodochalcones
rongalite dosage to 4 equiv. showed no further significant reaction bearing fluoro, chloro, bromo, phenyl, and alkynyl substituents (R1)
o
promotion (entry 18). Finally, decreasing the temperature to 90 C were successfully applied to the sulfonylation process, giving the
slightly obstructed the reaction (entry 19). In order to further corresponding products in excellent yields (3ad-3ah). In order to test
improve the catalytic efficiency of the reaction and decrease the whether the alkyl-substituted 2’-iodochalcones compatible with our
dosage of copper salt, we tested a series of ligands used to method, we conducted the reaction with 1ai and 1aj. To our
participate in the copper catalyzed coupling between aryl halides and satisfaction, the corresponding alkyl-substituted products 3ai and
aryl/alkyl sulfinates.17 However, after searching a series of amide- 3aj were also isolated from this process, although in a relative lower
type ligands, amino acid-type ligands and some other potential yield. However, for the 2’-bromochalcone substrate, less than 15%
ligands, we found there is no ligand have a better performance than yield was obtained and most of the starting materials were recovered
1,10-phenanthroline (See Supporting Information).
(See Supporting Information).
Table 1. Optimization of Reaction Conditionsa,b
Scheme 2. Synthesis of 1-thiaflavanone sulfones using rongalite.a,b
O
O
O
O
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
CH3CN, 110 oC, 8h
[Cu] (20 mol %)
O
O
S
R2
Ligand (24 mol %)
+
HO
R1
+
R2
HO
S
R1
Additive (1.0 equiv.)
Solvent, 110 oC, 8h
ONa 2H2
O
ONa 2H2O
S
S
I
X
O
O
O
O
1a
1
2
3a
2
3
X=I, Br
O
O
S
O
S
O
Yieldb
(%)
11
10
16
R2
Entry Cu catalyst
ligand
additive solvent
S
S
O
O
O
O
O
O
O
O
O
, R2=H (82%)
3i
, 84% yield
3a
3g
3h
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16c
17d
18e
19
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
CuCl
-
-
-
-
-
-
-
-
DMF
DMSO
CH3CN
, 74% yield
, 78% yield
, R2=4-Me (X=I, 77%; X=Br,14%c)
O
O
3b
O
, R2=4-Et (80%)
3c
, R2=4-tBu (76%)
O
O
O
O
3d
S
S
S
O
O
O
O
O
O
, R2=2-Me (72%)
3e
-
-
-
Toluene trace
O
, R2=3-Me (81%)
3j
3k
3l
3f
, 80% yield
, 88% yield
, 82% yield
NMP
trace
42
51
67
56
48
72
61
55
76
73
64
82
81
75
O
O
O
S
O
O
1,10-phen
1,10-phen
1,10-phen Bu4NCl
1,10-phen Bu4NBr
1,10-phen
1,10-phen
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
1,10-phen Bu4NCl
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
R2
Bu4NF
Br
S
S
O
O
O
O
S
O
O
O
O
O
O
CF3
, R2=4-F (74%)
, R2=4-Cl (77%)
, R2=4-Br (84%)
3o
3p
O
Br
, 80% yield
3n
, 81% yield
3m
, 79% yield
3r
3q
O
Bu4NI
DMSO
O
O
O
CH3
S
NO2
O
O
S
S
S
CuBr
CuI
O
O
O
O
O
O
NO2
CF3
Br
3t
3u
3v
, 69% yield
, 74% yield
, 79% yield
3s
, 77% yield
O
Cu(OTf)2
Cu(BF4)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
Cu(OTf)2
O
O
O
S
Ar
S
S
S
O
O
O
O
O
O
O
O
3y
, Ar=2-naphthyl (82%)
N
N
S
3z
3aa
, Ar=2-furanyl (83%)
3w
3x
, 86% yield
O
, 81% yield
3ab
, 75% yield
, Ar=2-thiophenyl (80%)
O
O
O
F
Br
Cl
S
S
S
S
O
O
aReaction conditions: 1a (0.20 mmol), rongalite 2 (0.40 mmol), Cu
catalyst (20 mol %), ligand (24 mol %), additive (1.0 equiv.), solvent
(2.0 mL), 110 oC, 8h. bIsolated yield based on 1a. cUsing 1.0 equiv. of
rongalite. dUsing 3.0 equiv. of rongalite. eUsing 4.0 equiv. of rongalite.
f90 oC.
O
O
O
O
O
O
O
O
O
3ad
, 81% yield
3ac
, 77% yield
3ae
, 80% yield
3af
, 82% yield
O
O
S
O
S
S
R'
O
, R'= Bu (56%)
, R'=nBu (37%)
O
O
O
t
3ai
3aj
O
O
O
3ag
, 78% yield
O
3ah
, 74% yield
With optimal conditions in hand, we next explored the substrate
scope of this sulfonylation process (Scheme 2). 2’-iodochalcones
bearing alkyl substituents showed good reactivity, generating
corresponding products 3a-3h in good yields. Furthermore, 2’-
iodochalcones bearing electron-donating groups gave excellent
yields (3i-3m). Notably, steric hindrance had little effect on the
reactivity. For example, di-ortho-substituted substrates 1g and 1m
reacted smoothly to give corresponding products 3g and 3m in good
aReaction conditions: 1 (0.20 mmol), 2 (0.60 mmol), Cu(OTf)2 (20 mol
%), 1,10-phen (24 mol %), Bu4NCl (1.0 equiv.), CH3CN (2.0 mL), 110
oC, 8 h. bIsolated yield based on 1.c130 oC, 24h.
A gram-scale experiment (using 5 mmol of substrate 1b) was con-
ducted to evaluate the applicability of this process. Gratifyingly,
product 3b was isolated in 65% yield under the optimized conditions.
Furthermore, product 3b can be readily functionalized to obtain
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
other derivatives. For example, 3b was reduced to 4b using excess bond coupling product was observed, while dehalogenated by-
NaBH4 in EtOH at 0 C. Furthermore, saturated 3b was oxidized to product 1eb was detected with 82% 1ea DreOcIo: 1v0e.r1e0d39Vi/(eDSwc0hACretCimc0le5eO8n04l0icn)Ae.
o
These results indicated that the initiation of intermolecular C-S
coupling between rongalite and 2’-iodochalcone maybe not favored,
and the dehalogenated by-product 1eb can be interpreted as direct
protonolysis of C-Cu species (Further control experiments see
Supporting Information). In addition, in the reaction of rongalite and
1fa, we found most of the starting material recovered instead of the
thia-Michael addition between 1fa and 2 (Scheme 4d). This result
may cause by the reversibility of thia-Michael addition,18 and the
formation of 1fb can be explained by the reducing properties of
rongalite via single electron transfer (See Supporting
Information).16,19 Besides, when we used carbonyl reduced 2’-
iodochalcone 8 to react with rongalite, desired sulfonylation product
was not obtained and most of the starting material were recovered
(Scheme 4e). Therefore, an initial thia-Michael reaction should be
reasonable according to the above experiments.
conjugate product 5b in the presence of I2/H2SO4 (1：1 mixture) in
DMSO (Scheme 3).
O
O
+
HO
S
ONa 2H2
O
I
1b
2
1.74g (5 mmol)
(3 equiv.)
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
CH3CN, 110 oC, 8h
O
OH
S
O
NaBH4
EtOH, 0 oC, 1h
I2, H2SO4
DMSO, 100 o
C
S
S
O
O
O
O
O
O
5b
3b
4b
99%
65%
91%
Scheme 3. Gram-scale synthesis and further transformation.
To make this process more practical, we examined its compati-
bility with thiourea dioxide, which can be converted into urea and
sulfur dioxide anion in the presence of base,16c,d for the construction
of 1-thiaflavanone sulfones. To our delight, under the same reaction
conditions, simply replacing rongalite with thiourea dioxide (2 equiv.)
and NaOH (2 equiv.), the reaction proceeded smoothly, giving the
corresponding products in moderate to good yields. When the
substrates were varied, different functional groups were mostly
tolerated, even halogen groups and heterocycles. (See Supporting
Information).
O
O
S
O
O
[Cu]
I
O
[Cu]
O
I
S
O
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
Cu
O
O
I'
O
O
S
III'
(a)
HO
+
ONa 2H2
O
CH3CN
110 oC, 8h
additive (1.0 equiv.)
S
I
O
O
1b
2
3b
O
S
HO
OH
O
ONa 2H2
O
-HCHO
[Cu]
O O
S
I
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
O
O
II'
O
+
S
O
S
(b)
(c)
ONa
Scheme 5. Proposed mechanism.
CH3CN
110 oC, 8h
I
O
6
1b
7,61%
Based on the results of the control experiments and previous
work,20 a plausible mechanism for this sulfonylation cascade was
proposed (Scheme 5). Initially, the coordination between 2’-
iodochalcone and copper catalyst gives intermediate I. A reversible
thia-Michael addition then leads to intermediate II, which is followed
by C-S bond coupling to give the target product via intermediate III.
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
I
I
O
S
+
HO
ONa 2H2
O
1eb
CH3CN
1ea
82% recovered
110 oC, 8h
Detected by GC-MS
1ea
2
O
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
1fa
O
O
81% recovered
Bu4NCl (1.0 equiv.)
+
HO
S
ONa 2H2
(d)
2-
O
O
CH3CN
110 oC, 8h
In conclusion, we have developed a novel SO2 incorporation
1fa
2
cascade for the synthesis of 1-thiaflavanone sulfone derivatives
under copper-catalyzed conditions. This sulfonylation proceeded to
achieve in situ incorporation of sulfone cores through the
consecutive formation of two C-S bonds. Furthermore, rongalite and
thiourea dioxide are low-cost and readily available sulfur dioxide
anion equivalents, making the reaction more economical and
environmentally friendly compared with other alternatives. This
method could become a commonly used approach for the synthesis
of 1-thiaflavanone sulfones, avoiding the use of toxic SO2 gas and
expensive SO2 surrogates as sulfone sources.
1fb
Detected by GC-MS
OH
I
CF3
8
OH
I
Cu(OTf)2 (20 mol %)
1,10-phen (24 mol %)
Bu4NCl (1.0 equiv.)
92% recovered
O
OH
+
HO
S
ONa 2H2
(e)
O
CH3CN
110 oC, 8h
CF3
8
2
S
O
O
9
CF3
Not detected
Scheme 4. Control experiments.
In order to understand the mechanism of this sulfonylation
reaction, a series of control experiments were conducted (Scheme 4).
When 2’-iodochalcone 1b was treated with rongalite in the presence
We are grateful to the National Natural Science Foundation of China
(Grant Nos. 21971080, 21971079 and 21772051) and the
Fundamental Research Funds for the Central Universities for
financial support. This work was also supported by the 111 Project
B17019.
of
2,2,6,6-tetramethyl-1-piperidinyloxy
(TEMPO)
or
butylhydroxytoluene (BHT), no marked decrease in the yield of 3b
was observed, which suggested that this transformation did not
involve a radical process (Scheme 4a). Next, rongalite was displaced
with sodium methanesulfinate (6) and added to the reaction, the
corresponding C-S coupling compound 7 was isolated in 61% yield
(Scheme 4b). However, when we used 2-iodonaphthalene (1ea) to
react with rongalite under the optimized conditions, no desired C-S
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
14 (a) S. Kotha and P. Khedkar, Chem. Rev., 2012, 112, 1650; (b)
Notes and references
View Article Online
D. Zheng and J. Wu, Sulfur Dioxide Insertion Reactions for
DOI: 10.1039/D0CC05800A
1
(a) J. Drews, Science., 2000, 287, 1960; (b) D. A. Smith and R.
M. Jones, Curr. Opin. Drug Discovery Dev., 2008, 11, 72; (c) N.
A. McGrath, M. Brichacek and J. T. Njardarson, J. Chem. Educ.,
2010, 87, 1348; (d) J. A. Southers, J. N. Bauman, D. A. Price, P.
S. Humphries, G. Balan, J. F. Sagal, T. S. Maurer, Y. Zhang, R.
Oliver, M. Herr, D. R. Healy, M. Li, B. Kapinos, G. D. Fate, K. A.
Riccardi, V. M. Paralkar, T. A. Brown and A. S. Kalgutkar, ACS
Med. Chem. Lett., 2010, 1, 219; (e) J. I. Montgomeryet al., J.
Med. Chem., 2012, 55, 1662; (f) P. Das, M. D. Delost, M. H.
Qureshi, D. T. Smith and J. T. Njardarson, J. Med. Chem., 2018,
62, 4265; (g) K. A. Scott and J. T. Njardarson, Top. Curr. Chem.,
2018, 376, 5.
(a) G. J. Wells, M. Tao, K. A. Josef and R. Bihovsky, J. Med.
Chem., 2001, 44, 3488; (b) S. H. Kimet al., Bioorg. Med. Chem.
Lett., 2008, 18, 4181; (c) K. K. C. Liu, S. Bailey, D. M. Dinh, H.
Lam, C. Li, P. A. Wells, M. J. Yin and A. Zou, Bioorg. Med. Chem.
Lett., 2012, 22, 5114; (d) H. Rueeger, R. Lueoend, O. Rogel, J.
M. Rondeau, H. Möbitz, R. Machauer, L. Jacobson, M.
Staufenbiel, S. Desrayaud and U. Neumann, J. Med. Chem.,
2012, 55, 3364; (e) E. A. Ilardi, E. Vitaku and J. T. Njardarson,
J. Chem. Educ., 2013, 90, 1403.
Organic Synthesis, Nature Springer, Berlin, 2017.
15 For selected examples see: (a) S. Kotha, P. Khedkar and A. K.
Ghosh, Eur. J. Org. Chem., 2005, 3581; (b) A. Shavnya, S. B.
Coffey, K. D. Hesp, S. C. Ross and A. S. Tsai, Org. Lett., 2016,
18, 5848; (c) S. Kotha and G. Sreevani, ChemistrySelect., 2017,
2, 10804; (d) V. D. Nguyen, V. T. Nguyen, G. C. Haug, H. T. Dang,
H. D. Arman, W. C. Ermler and O. V. Larionov, ACS Catal., 2019,
9, 4015.
16 For selected examples see: (a) W. Zhang and M. Luo, Chem.
Commun., 2016, 52, 2980; (b) M. Wang, B. C. Tang, J. G. Wang,
J. C. Xiang, A. Y. Guan, P. P. Huang, W. Y. Guo, Y. D. Wu and A.
X. Wu, Chem. Commun., 2018, 54, 7641; (c) S. Ye, Y. Li, J. Wu
and Z. Li, Chem. Commun., 2019, 55, 2489; (d) S. Chen, Y. Li,
M. Wang and X. Jiang, Green Chem., 2020, 22, 322.
17 For ligands used to participated in the copper-cataltzed C-S
bond coupling between aryl halides and aryl/alkyl sulfinates
see: (a) J. M. Baskin and Z. Wang, Org. Lett., 2002, 4, 4423; (b)
W. Zhu and D. Ma, J. Org. Chem., 2005, 70, 2696; (c) M. Yang,
H. Shen, Y. Li, C. Shen and P. Zhang, RSC Adv., 2014, 4, 26295;
(d) D. Ma, S. Niu, J. Zhao, X. Jiang, Y. Jiang, X. Zhang and T. Sun,
Chin. J. Chem., 2017, 35, 1661; (e) X. Ge, F. Sun, X. Liu, X. Chen,
C. Qian and S. Zhou, Molecular Catalysis, 2018, 449, 72; (f) J.
Zhao, S. Niu, X. Jiang, Y. Jiang, X. Zhang, T. Sun and D. Ma, J.
Org. Chem., 2018, 83, 6589; (g) Y. Peng, Journal of Chemical
Research, 2014, 38, 447; (h) B. T. V. Srinivas, V. S. Rawat, K.
Konda and B. Sreedhar, Adv. Synth. Catal., 2014, 356, 805.
18 L. Li, Y. Liu, Y. Peng, L. Yu, X. Wu and H. Yan, Angew. Chem. Int.
Ed., 2015, 55, 331.
2
3
4
(a) T. H. Huang, J. Lin, L. Y. Chen, Y. T. Lin and C. C. Wu, Adv.
Mater., 2006, 18, 602; (b) Y. Shirota and H. Kageyama, Chem.
Rev., 2007, 107, 953; (c) A. Mishra, C. Q. Ma and P. Bäuerle,
Chem. Rev., 2009, 109, 1141; (d) L. Duan, J. Qiao, Y. Sun and
Y. Qiu, Adv. Mater., 2011, 23, 1137; (e) S. Chen, Y. Yang, Y. Wu,
H. Tian and W. Zhu, J. Mater. Chem., 2012, 22, 5486; (f) M. E.
Cinar and T. Ozturk, Chem. Rev., 2015, 115, 3036.
X. Y. Qin, L. He, J. Li, W. J. Hao, S. J. Tu and B. Jiang, Chem.
Commun., 2019, 55, 3227.
19 (a) F. Yu, R. Mao, M. Yu, X. Gu and Y. Wang, J. Org. Chem.,
2019, 84, 9946; (b) M. Wang, B. C. Tang, J. C. Xiang, X. L. Chen,
J. T. Ma, Y. D. Wu and A. X. Wu, Org. Lett., 2019, 21, 8934; (c)
S. Golla, S. Poshala, R. Pawar and H. P. Kokatla, Tetrahedron
Lett., 2020, 61, 151539.
20 (a) R. Kerber and J. Starnick, Chem. Ber., 1971, 104, 2035; (b)
R. Kerber and W. Gestrich, Chem. Ber., 1973, 106, 798.
5
6
7
8
M. Wang, S. Chen and X. Jiang, Org. Lett., 2017, 19, 4916.
Q. Yao, Org. Lett., 2002, 4, 427.
A. Rodríguez and W. J. Moran, J. Org. Chem., 2016, 81, 2543.
Q. G. Wang, Q. Q. Zhou, J. G. Deng and Y. C. Chen, Org. Lett.,
2013, 15, 4786.
(a) M. S. Hossain and A. L. Schwan, Org. Lett., 2011, 13, 5330;
(b) J. P. John and A. V. Novikov, Org. Lett., 2007, 9, 61; (c) C.
Bosset, G. Lefebvre, P. Angibaud, I. Stansfield, L. Meerpoel, D.
Berthelot, A. Guérinot and J. Cossy, J. Org. Chem., 2016, 82,
4020; (d) Y. Luo, X. Pan, C. Chen, L. Yao and J. Wu, Chem.
Commun., 2015, 51, 180; (e) A. F. Wang, W. J. Hao, Y. L. Zhu,
G. Li, P. Zhou, S. J. Tu and B. Jiang, ACS Omega, 2018, 3, 1482.
9
10 R. Mao, D. Zheng, H. Xia and J. Wu, Org. Chem. Front., 2016,
3, 693.
11 For selected examples see: (a) M. H. Holshouser, L. J. Loeffler
and I. H. Hall, J. Med. Chem., 1981, 24, 853; (b) P. Johnson and
R. J. Taylor, Tetrahedron Lett., 1997, 38, 5873; (c) W. Zhou and
E. L. Clennan, J. Am. Chem. Soc., 1999, 121, 2915; (d) T.
Patonay, W. Adam, A. Lévai, P. Kövér, M. Németh, E. M. Peters
and K. Peters, J. Org. Chem., 2001, 66, 2275; (e) C. Yang, Q. Jin,
H. Zhang, J. Liao, J. Zhu, B. Yu and J. Deng, Green Chem., 2009,
11, 1401; (f) N. Fukuda and T. Ikemoto, J. Org. Chem., 2010,
75, 4629; (g) M. Jereb, Green Chem., 2012, 14, 3047; (h) R.
Afrasiabi, M. R. Farsani and B. Yadollahi, Tetrahedron Lett.,
2014, 55, 3923; (i) S. Ghosh and S. Athe, Synthesis, 2016, 48,
917.
12 S. Sangeetha, P. Muthupandi and G. Sekar, Org. Lett., 2015, 17,
6006.
13 (a) A. Ouchi, T. Obata, T. Oishi, H. Sakai, T. Hayashi, W. Ando
and J. Ito, Green Chem., 2004, 6, 198; (b) N. Chappell, J. Soc.
Dyers Colour., 1921, 37, 206; (c) J. J. Robillard,
US2004259975A1, 2004; Chem. Abstr., 2004, 142, 76344; (d)
C. Fang, Y. Li and Z. Liu, CN101301268A, 2008; Chem. Abstr.,
2008, 150, 24159; (e) W. Hacke and H. Horn, US4386083A,
1983; Chem. Abstr., 1983, 99, 76879.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC05800A
2-
SO2
O
O
I
O
R1
[Cu]
R'
HO
S
+
R1
ONa 2H2O
S
R'
O
O
Rongalite(~0.03$/g)
industrial product
R'=aryl, alkyl
36 examples
Rongalite:A cheap sulfone source
C(aryl)-S bond formation
Six-Membered cyclization
Gram scale synthesis