Visible-light-mediated difunctionalization of vinylcyclopropanes for the synthesis of 1-sulfonylmethyl-3,4-dihydronaphthalenes

Article abstract of DOI:10.1039/c9ob01321k

An efficient method for visible-light-mediated sulfonylation/arylation of the C-C σ-bond in vinylcyclopropanes with sulfonyl chlorides to synthesize 1-sulfonylmethyl-substituted 3,4-dihydronaphalenes has been developed. A radical-type pathway has been proved in this transformation. This difunctionalization procedure shows a series of advantages, such as the use of commercially and easily available sulfonyl chlorides, mild conditions, and eco-friendly energy.

Full text of DOI:10.1039/c9ob01321k

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Q. Wang, W.
Zhang, Q. Zhou, C. Zhou, B. Xiong, K. Tang and Y. Liu, Org. Biomol. Chem., 2019, DOI:
10.1039/C9OB01321K.
Volume 15
Number 47
21 December 2017
Pages 9945-10124
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
Accepted Manuscripts are published online shortly after acceptance,
rsc.li/obc
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
ISSN 1477-0520
PAPER
I . J. Dmochowski et al.
Oligonucleotide modifi cations enhance probe stability for
shall the Royal Society of Chemistry be held responsible for any errors
single cell transcriptome in vivo analysis (TIVA)
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
rsc.li/obc

Page 1 of 9
Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C9OB01321K
ARTICLE
Visible-light-mediated difunctionalization of C−C bond for the
synthesis of 1-sulfonylmethyl-3,4-dihydronaphthalenes
Received 00th January 20xx,
Accepted 00th January 20xx
Qiao-Lin Wang,† Wen-Zheng Zhang,† Quan Zhou, Cong-Shan Zhou, Bi-Quan Xiong, Ke-Wen Tang,
Yu Liu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient visible-light-mediated sulfonylation/arylation of C−C Pyroxasulfone (KIH-485), a heteroaryl alkyl sulfone, is a novel pre-
σ–bond in vinylcyclopropanes with sulfonyl chlorides to synthesize emergence herbicide with low toxicity and high efficiency3b. The (+)-
1-sulfonylmethyl-substituted 3,4-dihydronaphalenes is developed. thiamphenciol, an aryl alkyl sulfone, is a kind of bacteriostatic agent,
A radical-type pathway has been proved in this transformation. especially in the aspect of Gram-negative and Gram-positive
This difunctionalization procedure shows a series of advantages, microorganisms. Additionally, (+)-thiamphenciol has a series of
such as using commercially and easily available sulfonyl chlorides, advantages, such as broad-spectrum antibacterial activity, excellent
mild conditions and eco-friendly energy.
tissue distribution, the potential for oral administration, and low
toxicity3c. The cholic acid derivative, an aryl alkyl sulfone, has a good
application in the treatment of cholecystitis, bile deficiency and
intestinal dyspepsia3d. However, based on all of the reported
interesting structures and application of sulfones, efficient and
convenient methods for accessing sulfone-containing compounds
are urgent need.
Introduction
Sulfones are extremely important organosulfur compounds in
pharmaceutical industry and agriculture industry1-2. A great deal of
attention has been paid to introduce sulfone skeletons into organic
molecules, which displayed a unique application value in polymer
materials, organic synthesis, medicinal chemistry, and agrochemical
communities3. As shown in Scheme 1, dapsone (4,4’-
diaminodiphenyl sulfone), an aryl sulfone, is widely used in the
treatment of bacterial infections, especially in the killing of
Mycobacterium leprae3a.
In the past several decades, the introduction of sulfur-
containing group, especially sulfonyl groups, into organic molecules
has captured generous chemists’ attentions4,5. Among the common
sulfonyl sources, sulfonyl chlorides are a class of cheap, abundant
and easily available sulfonyl sources, and have a wide application in
organic chemical and pharmaceutical engineer. Sulfonyl chlorides
could undergo sulfonylation reactions to afford sulfur−carbon
bonds or sulfur−hetero bonds (Scheme 2)6,7. In 2018, our group7a
reported the visible-light-mediated difunctionalization of active
alkynes with sulfonyl chlorides under mild conditions (path I). In
F3C
O
O
N
O
O
S
N
S
H2N
NH2
OCHF2
N
O
2017, Ni’s7b group presented
a visible-light-catalyzed direct
Dapsone
KIH-485
Aczone antibiotic
pre-emergence herbicide
oxidative sulfonylation of alkenes with sulfonyl chlorides for the
preparation of β-keto sulfones (path II). In 2013, Wu et al.7c
reported a novel copper-catalyzed cross-coupling of quinolone N-
oxides with sulfonyl chlorides for constructing sulfonylated
quinolone N-oxides (path III). In 2016, Reiser and co-workers7d
reported the hydroxylsulfonylation of styrenes with sulfonyl
chlorides for the synthesis of β-hydroxysulfones by visible-light-
catalysis (path IV). This transformation proceeded via an ATRA
(atom transfer radical addition) process. This group7e also presented
the visible-light-mediated sulfonylation of heterocyclic compounds
with sulfonyl chlorides for constructing sulfonylated heterocyclic
compounds (path V). Wu’s group7f presented a mild and novel
copper-catalyzed C5−H sulfonylation of 8-aminaquinoline amides
with excellent functional tolerance (path VI). However, transition-
metal catalysts, strong oxidants, bases and ligands are inevitably
O
OH
HN
OMe
Q
OH
CHCl2
N
H
H
S
S
O
Ph
O
O
O
H
H
O
MeO
OMe
H
(+)-thiamphenciol
bacteriostatic agents
cholic acid derivative
Scheme 1 Selected drugs containing the sulfone moiety
*Department of Chemistry and Chemical Engineering, Hunan Institute of Science
and Technology, Yueyang 414006, China
E-mail: lyxtmj_613@163.com
† These authors contributed equally to this work.
** Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. 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
Organic & Biomolecular Chemistry
Page 2 of 9
Organic & Biomolecular Chemistry
PAPER
involved in most of these transformations. Thus, environmentally- reactions were conducted with other light sources, such as 36 W
View Article Online
friendly, safe, simple and mild sulfonylation methods are lacking.
compact fluorescent light, 3 W blue LED lighDt OorI:510W.10g3r9e/eCn9OLEBD01l3ig21hKt
(entries 9−11). The reaction employing 1 mol% Ru(bpy)3Cl2 and a 12
W blue LEDs only afforded the product 3aa in 36% yield (entry 12).
The effect of the base was examined. However, several other bases,
such as K2CO3, Na2CO3, Cs2CO3, pyridine and Et3N were less effective
than 2,6-lutidine (entries 13−17). The reaction could deliver 63%
yield in the presence of Na2CO3 (entry 14). No obvious
improvement of yield was observed when a series of other solvents,
including CH3CN, THF, DMF, DMSO and toluene, were used in this
transformation (entries 18−22). Using THF in the reaction afforded
the product 3aa in 74% yield (entry 19).
R3
Z
R1
R3
O
R
O
O
R
O
N
R2
O
S
R1
HO
R1
S
Ar
R2
O
Eosin Y, Na2CO3
H O
fac[Ir(ppy)3]
MeCN : H2O (5 : 1)
Ar
R2
N
R2
, CH3CN, Ar, 100 oC
O
R1
2
LED455, r.t., 12 h
5 W blue LED light, 24 h
path IV
path I
Y
O
O
R
R
O
S
R1
R
Y
S
X
R1
RSO2Cl
R
Ir(dtbbpy)(ppy)2PF6
O
fac[Ir(ppy)3], Na2CO3
X
O
visible light, air, CH3CN
LED455, r.t., 48 h, N2
path II
path V
R
S
R1
O
O
R1
N
R1
N
H
O
O
N
O
S
N
Table 1 Screening of optimal reaction conditionsa
R
CuI, K2CO3
CuI, K2CO3
O
R1
DCE, 100 oC, 24 h, air
DCE, 100 oC, 24 h
path III
path VI
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
O
O
S
Scheme 2 Selected sulfonylation reactions by using sulfonyl
chlorides as sulfonyl sources
S
+ Ph
Cl
Ph
O
5 W blue LED light
O
Ar, 24 h, 100 o
C
Recently, visible-light-catalysis has become an efficient and
fascinating tool in organic transformations because of its
environmentally benign sustainability, high efficiency and mild
operating conditions8. Additionally, the methods for ring-opening
and cyclization of vinylcyclopropanes were very few9. Therefore,
based on our work in the aspect of sulfonylation reactions10a-10c and
visible-light-catalysis reactions10c-10i, we presented a visible-light-
1a
3aa
2a
Entry
Variation from the standard conditions
Yield (%)b
83
1
2
none
Ir(ppy)3 instead of Ru(bpy)3Cl2
Eosin Y instead of Ru(bpy)3Cl2
Na2-Eosin Y instead of Ru(bpy)3Cl2
without Ru(bpy)3Cl2
without additional light
Ru(bpy)3Cl2 (10 mol%)
Ru(bpy)3Cl2 (2 mol%)
none
78
56
35
0
3
4
5
promoted
vinylcyclopropanes with sulfonyl chlorides for the preparation of 1-
sulfonylmethyl-3,4-dihydronaphalenes, which achieved by
sulfonylation/arylation
of
C−C
σ–bond
in
6
0
7
85
68
33
25
31
36
47
63
22
39
26
69
74
22
29
41
71
66
57
84
72
8
9c
difunctionalization of C−C σ–bonds in cyclopropyl olefins with a
sulfonyl radical and an aromatic carbon (Scheme 3).
10d
11e
12f
13
14
15
16
17
18
19
20
21
22
23
24
25
26g
none
none
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
Ru(bpy)3Cl2 (1 mol%)
K2CO3 instead of 2,6-lutidine
Na2CO3 instead of 2,6-lutidine
Cs2CO3 instead of 2,6-lutidine
pyridine instead of 2,6-lutidine
Et3N instead of 2,6-lutidine
CH3CN instead of 1,4-dioxane
THF instead of 1,4-dioxane
DMF instead of 1,4-dioxane
DMSO instead of 1,4-dioxane
toluene instead of 1,4-dioxane
110 oC
R1
O
O
S
S
+
R2
Cl
R2
R1
O
5 W blue LED light
O
Ar, 24 h, 100 o
C
Scheme 3 Oxidative radical difunctionalization of C–C σ–bonds in
vinylcyclopropanes
Results and discussion
In an initial attempt to clarify the optimal reaction conditions, we
chose (1-cyclopropylvinyl)benzene 1a and benzenesulfonyl chloride
2a as model substrates. To our delight, the desired product 4-
90 oC
80 oC
none
(phenylsulfonylmethyl)-1,2-dihydronaphthalene
3aa
was
27h
none
successfully obtained in 83% yield by using Ru(bpy)3Cl2 (5 mol%) as
catalysts, 2,6-lutidine (2 equiv) as base in 1,4-dioxane (2 mL) at 100
oC under 5 W blue LED irradiation for 24 h. Encouraged by this
result, a series of other visible-light catalysts, including Ir(ppy)3,
Eosin Y and Na2-Eosin Y were examined (entries 2−4). Unfortunately,
all of these catalysts could not increase the reaction yields obviously.
Additionally, the reaction could not deliver the product 3aa in the
absence of catalyst or light irradiation (entries 5−6). Next, the
amount of catalyst was investigated. The reaction performed with
10 mol% of Ru(bpy)3Cl2 gave similar yield with that using 5 mol% of
Ru(bpy)3Cl2 and reducing the amount to 2 mol% led to a lower yield
(entries 7−8). The yields of the reactions decreased when the
a
Reaction conditions: 1a (0.2 mmol), 2a (2 equiv, 0.4 mmol),
Ru(bpy)3Cl2 (5 mol%, 0.01 mmol), 2,6-lutidine (2 equiv, 0.4
mmol) in 1,4-dioxane (2 mL) at 100 oC under an argon
atmosphere and 5 W blue LED light for 24 h. b isolated yield. c 36
W compact fluorescent light instead of 5 W blue LED light. d 3 W
e
blue LED light instead of 5 W blue LED light. 5 W green LED
f
g
light instead of 5 W blue LED light. 12 W blue LEDs. 36 h
instead of 24 h. h 1a (1 g, 4.24 mmol) and solvent (10 mL) for 72
h.
Notably, the yield of the desired product 3aa decreased to 71%
when the oil bath temperature increased to 110 C (entry 23), and
the reaction carried out at 90 oC or 80 oC generated the desired
o
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
Organic & Biomolecular Chemistry
Please do not adjust margins
Organic & Biomolecular Chemistry
PAPER
product 3aa in low yields (entries 24−25). Additionally, the reaction under the standard conditions could not generate the target
View Article Online
DOI: 10.1039/C9OB01321K
yield did not increase obviously when the reaction was performed product (product 3ar). Notably, several aliphatic sulfonyl chlorides,
for a longer time (entry 26). To our delight, a scale-up reaction including dodecane-1-sulfonyl chloride 2t and ethanesulfonyl
could successfully afford the product 3aa in 72% yield (entry 27).
chloride 2u could afford the target product in good yields (products
3at and 3au).
Table 2 Scope of cyclopropyl olefins (1) and sulfonyl chlorides (2)a
Next, we turn our attention to investigate the scope of
cyclopropyl olefins 1 in the presence of 4-chlorobenzene-1-sulfonyl
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
Cl
o
R1
chloride 2f, Ru(bpy)3Cl2, 2,6-lutidine in 1,4-dioxane at 100 C under
O
O
S
S
+
R2
Cl
R2
5 W blue LED irradiation for 24 h. A series of cyclopropyl olefins
were examined and these reactions could proceed smoothly to
deliver the sulfonylation/arylation products in moderate to good
yields (products 3bf–pf). However, the cyclopropyl olefins 1c with
an meta-substituted aryl group could undergo this
difunctionalization smoothly and the products 4-(((4-
chlorophenyl)sulfonyl)methyl)-6-methyl-1,2-dihydronaphthalene
R1
Ar =
O
5 W blue LED light
O
Ar, 24 h, 100 o
C
1
2
3
R
O
O
O
O
S
S
S
S
O
O
O
O
R
3ak, 79%
R = Me, 3ab, 85%
R = OMe, 3ac, 89%
3ad, 91%
R = Me, 3al, 73%
R = CN, 3am, 65%
R = NO2, 3an, 40%
3ao, 70%
R = tBu,
R = F, 3ae, 80%
R =Cl, 3af, 73%
R = Br, 3ag, 67%
R = CF3, 3ah, 58%
R = Ac, 3ai, 63%
R = NO2, 3aj, 49%
3cf
and
4-(((4-chlorophenyl)sulfonyl)methyl)-8-methyl-1,2-
O
O
O
S
S
dihydronaphthalene 3cf’ could be obtained in 76% yield (3 : 1). The
cyclopropyl olefins with electron-donating substituted aryl groups
afforded high yields than which with electron-withdrawing
substituted aryl groups (products 3df–kf). To our delight, 2-(1-
cyclopropylvinyl)naphthalene 1l was suitable for this reaction
system and produced the major product 3lf in 70% yield. The
heteroaromatic substituted vinylcyclopropanes 1n–p could
successfully deliver the corresponding products 3nf–pf in moderate
yields. It's worth noting that the reaction of substrate 1n (3-(1-
cyclopropylvinyl)pyridine) only gave the product 3nf as major
product and another isomer was quite few. However, cyclopropyl
olefins 1m could not afford the target product 3mf in this
transformation. Another dehydrogenation product (5-(((4-
chlorophenyl)sulfonyl)methyl)isoquinoline 3mf’ could be obtained
in 65% yield. Additionally, vinylcyclobutane 1q was not compatible
with the standard conditions (product 3qf).
S
S
Bn
O
O
O
3ap, 65%
3aq, 53%
3ar, 0%b
OMe
O
S
O
S
O
R2
O
O
S
Ar
S
Ar
O
Ar
R2 = CF3, 3as, 0%
O
O
R2
R
=
nC12H25, 3at, 68%
3bf, 57%
3cf'
3cf
2 = C2H5, 3au, 63%
76%, 3cf / 3cf' = 3 : 1
R
N
O
O
O
O
S
N
S
S
S
Ar
Ar
Ar
Ar
O
O
O
O
O
3mf, 0% (65%c)
3nf, 55%
3lf, 70%
R = OMe, 3df, 82%
R = OBn, 3ef, 78%
R = Me, 3ff, 80%
R = tBu, 3gf, 84%
R = F, 3hf, 67%
R = Cl, 3if, 60%
R = Br, 3jf, 54%
R = CF3, 3kf, 61%
O
S
N
O
S
Ar
S
S
O
Ar
Ar
O
O
3pf, 43%
3of, 48%
3qf, 0%
a
Reaction conditions: 1 (0.2 mmol), 2 (2 equiv, 0.4 mmol),
Ru(bpy)3Cl2 (5 mol%, 0.01 mmol), 2,6-lutidine (2 equiv, 0.4
o
mmol) at 100 C under an argon atmosphere and 5 W blue LED
light for 24 h. b No other product was detected and most of the
c
starting materials was recovered.
chlorophenyl)sulfonyl)methyl)isoquinoline 3mf’.
The yield of (5-(((4-
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
5 W blue LED light
O
S
O
(1)
S
+ Ph
+ Ph
+ Ph
Cl
Cl
Cl
Ph
O
Ar, 24 h, 100 o
C
O
Having the established conditions in hand, the scope of sulfonyl
1a
1a
1a
2a
TEMPO (2 equiv)
3aa
3aa
, 18%
chlorides
2
were examined in the presence of (1-
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
5 W blue LED light
cyclopropylvinyl)benzene 1a under the optimized conditions (Table
2). We were delighted to find that a series of arylsulfonyl chlorides,
which connected with electron-withdrawing or electron-donating
groups on the aromatic rings, could successfully deliver the target
products in moderate to excellent yields (3ab–ap). The arylsulfonyl
chlorides with electron-rich groups delivered higher yields than that
with electron-deficient groups. Additionally, the steric effect also
had significant influence on the reaction yields according to the
experimental results, and the reactivity order for sulfonylation is
ortho < meta < para (products 3ab, 3ak, and 3al). Surprisingly, 4-
nitrobenzene-1-sulfonyl chloride 2j was suitable for this
sulfonylation/arylation and delivered the target product 4-((4-
nitrophenylsulfonyl)methyl)-1,2-dihydronaphthalene 3aj in 49%
yields. The 2,4,6-trimethylbenzene-1-sulfonyl chloride 2o was also
compatible for the standard conditions (product 3ao). It should be
noted that thiophene-2-sulfonyl chloride 2q was employed as
sulfonyl source in the present reaction systems and could lead to 1-
sulfonylmethyl-substituted 3,4-dihydronaphalene 3aq in 53% yield.
Unfortunately, using benzylsulfonyl chloride 2r as sulfonyl source
O
S
O
S
(2)
(3)
Ph
O
Ar, 24 h, 100 o
C
O
2a
BHT (2 equiv)
, 27%
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
1,4-dioxane (2 mL)
5 W blue LED light
O
O
S
Ph
S
3aa
+
Ph
O
Ph
20%
Ar, 24 h, 100 o
C
O
2a
4
, 63%
1,1-diphenylethylene (2 equiv)
Scheme 4 Control experiments.
To gain insights into the mechanism of this transformation, a
series of control experiments were performed (Scheme 4).
According to the previous literature, this difunctionalization of
cyclopropyl olefins and sulfonyl chlorides proceeded via a radical
process9,10b-10c. Several radical inhibitors such as TEMPO or BHT
were added into the reaction between 1a and 2a under the optimal
conditions (eqs 1−2, Scheme 4). Notably, all of these reactions were
obviously inhibited. When 1,1-diphenylethylene was added into the
reaction, the target difunctional product 3aa was obtained only in
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
Organic & Biomolecular Chemistry
Page 4 of 9
Organic & Biomolecular Chemistry
PAPER
20% yield, along with delivering (2-(phenylsulfonyl)ethene-1,1- synthesis and medicinal chemical is ongoing in our labVoireawtAorrtiycl.e Online
DOI: 10.1039/C9OB01321K
diyl)dibenzene 4 in 63% yield (eq 3, Scheme 4). The results
demonstrated that
difunctionalization.
A plausible mechanism was displayed in Scheme 5 inspired by
presented results and previous reports6-11. Initially, [Ru(bpy)3]2+ is
a
radical route was involved in this Experimental
General methods
All reactions were carried out with magnetic stirring and in dried
glassware. Standard syringe techniques were applied for transfer of
dry solvents. All reagents and solvents were commercially available
and used without any further purification unless specified. Proton
(1H NMR) and carbon (13C NMR) nuclear magnetic resonance
spectra were recorded at 400 MHz and 100MHz, respectively. The
chemical shifts are given in parts per million (ppm) on the delta (δ)
photoexcited by visible light to form
a strong reductant
[Ru(bpy)3]2+*, which can undergo a quenching reductive cycle. The
radical anion A is generated from benzenesulfonyl chloride 2a
under the action of [Ru(bpy)3]2+* via a SET process7a,7b,7d,7e,9. The
intermediate A performs decomposition to afford the sulfonyl
radical B. The radical addition of radical B to the terminal carbon of
double bond in vinylcyclopropane 1a delivers the stable benzyl
radical C. The experimental results of entries 23−25 in Table 1
suggested that the formation of benzyl radical C (including the
formation of the sulfonyl radical and the addition of the sulfonyl
radical to the double bond in vinylcyclopropanes) needed heating.
Next, the intermediate C proceeds homolytic cleavage of C−C σ–
bond in three-membered carbocyclic ring to generate the terminal
alkyl radical D. Then, it undergoes cyclization with the
intermolecular phenyl ring to give the aryl radical E, which is
oxidized into the aryl cation F by [Ru(bpy)3]3+. Finally, the target
product 3aa is produced by deprotonation of the intermediate F
under the action of base. Notably, quantum yield measurements of
this difunctionalization process (Φ = 0.016) suggested that radical
chain are not the major product-forming pathway in this
transformation11.
1
scale. The solvent peak was used as a reference value, for H NMR:
TMS = 0.00 ppm, for 13C NMR: CDCl3 = 77.00 ppm. The following
abbreviations were used to explain multiplicities: s = singlet, d =
doublet, dd = doublet of doublet, t = triplet, td = triplet of doublet,
q = quartet, m = multiplet, and br = broad. Analytical TLC was
performed on precoated silica gel plates. High-resolution mass
spectra (HRMS) were obtained on an Agilent mass spectrometer
using ESI-TOF (electrospray ionization-time of flight).
General procedure for the synthesis of 1-sulfonylmethyl-3,4-
dihydronaphthalenes 3
To a Schlenk tube were added 1a (0.2 mmol), 2a (2 equiv, 0.4
mmol), Ru(bpy)3Cl2 (5 mol %, 0.01 mmol), 2,6-lutidine (2 equiv, 0.4
mmol) in 1,4-dioxane (2 mL). Then the mixture was stirred at 100 oC
(oil bath temperature) in argon atmosphere (1 atm) under 5 W blue
LED light for 24 h until complete consumption of starting material
as monitored by TLC and GC-MS analysis. After the reaction was
finished, the reaction mixture was washed with brine. The aqueous
phase was re-extracted with EtOAc (3 × 10 mL). The combined
organic extracts were dried over Na2SO4 and concentrated in
vacuum. The residue was purified by silica gel flash column
chromatography (hexane/ethyl acetate = 10 : 1 to 1 : 1) to afford
the desired products 3.
O
-
Cl
O
S
O
Cl
Ph
-Cl-
S
O
1a
S
Ph
O
2a
Ph
O
O
S
O
Ph
A
B
SET
C
[Ru(bpy)3]3+
[Ru(bpy)3]2+
*
Redox-neutral Cycle
O
O
S
S
Ph
O
Ph
O
H
hv
4-((Phenylsulfonyl)methyl)-1,2-dihydronaphthalene (3aa): yellow
oil; H NMR (400 MHz, CDCl3) δ: 7.81 (d, J = 8.0 Hz, 2H), 7.55 (t, J =
D
SET
E
1
[Ru(bpy)3]2+
O
7.2 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.13-7.08 (m, 4H), 5.93-5.90 (m,
1H), 4.23 (s, 2H), 2.69 (t, J = 8.0 Hz, 2H), 2.25-2.20 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ: 138.3, 135.9, 135.0, 133.6, 128.8, 128.7, 128.7,
127.6, 127.4, 126.4, 125.8, 123.1, 60.0, 27.7, 23.3; HRMS (ESI-TOF)
m/z: C17H17O2S (M + H)+ calcd for 285.0944, found 285.0949.
O
- H+
S
S
Ph
Ph
base
O
H
O
F
3aa
Scheme 5 Proposed mechanism.
1
4-(Tosylmethyl)-1,2-dihydronaphthalene (3ab): yellow oil; H NMR
(400 MHz, CDCl3) δ: 7.68 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H),
7.14-7.05 (m, 4H), 5.92-5.89 (m, 1H), 4.20 (s, 2H), 2.69 (t, J = 8.0 Hz,
2H), 2.38 (s, 3H), 2.25-2.20 (m, 2H); 13C NMR (100 MHz, CDCl3) δ:
163.6, 135.8, 134.7, 132.6, 130.8, 129.8, 127.5, 127.2, 126.3, 126.0,
123.1, 113.9, 60.1, 55.6, 27.7, 23.3; HRMS (ESI-TOF) m/z: C18H19O2S
(M + H)+ calcd for 299.1100, found 299.1106.
4-(((4-Methoxyphenyl)sulfonyl)methyl)-1,2-dihydronaphthalene
(3ac): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.72-7.68 (m, 2H),
7.11-7.07 (m, 4H), 6.88-6.85 (m, 2H), 5.92-5.90 (m, 1H), 4.19 (s, 2H),
3.82 (s, 3H), 2.71-2.63 (m, 2H), 2.25-2.20 (m, 2H); 13C NMR (100
MHz, CDCl3) δ: 163.7, 135.9, 134.8, 132.7, 130.9, 129.9, 127.6, 127.3,
Conclusion
In conclusion,
a
mild and facile visible-light-mediated
sulfonylation/arylation of C−C σ–bond in cyclopropyl olefins with
sulfonyl chlorides for accessing 1-sulfonylmethyl-substituted 3,4-
dihydronaphalenes is developed. Our investigations show that this
C−C σ–bond sulfonylation/arylation contains a radical pathway. This
novel method has the advantages of using commercially and easily
available sulfonyl chlorides, mild conditions, and eco-friendly
energy. This C−C σ–bond sulfonylation/arylation involves a series of
sulfonyl radical addition, radical rearrangement and C−C bond
formation. A wide application of this new method in organic
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
Organic & Biomolecular Chemistry
Please do not adjust margins
Organic & Biomolecular Chemistry
PAPER
126.4, 126.1, 123.2, 114.0, 60.2, 55.7, 27.8, 23.3; HRMS (ESI-TOF) 122.8, 60.0, 27.6, 23.3; HRMS (ESI-TOF) m/z: C17H16NO4S (M + H)+
View Article Online
m/z: C18H19O3S (M + H)+ calcd for 315.1049, found 315.1055.
calcd for 330.0795, found 330.0800.
DOI: 10.1039/C9OB01321K
4-(((4-(tert-Butyl)phenyl)sulfonyl)methyl)-1,2-dihydronaphthalene 4-((m-Tolylsulfonyl)methyl)-1,2-dihydronaphthalene (3ak): yellow
1
(3ad): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.70 (d, J = 8.4 Hz, 2H), oil; H NMR (400 MHz, CDCl3) δ: 7.55-7.48 (m, 2H), 7.25-7.19 (m,
7.38 (d, J = 8.8 Hz, 2H), 7.05-7.04 (m, 2H), 7.00-6.98 (m, 2H), 6.03- 2H), 7.06-6.97 (m, 4H), 5.88-5.86 (m, 1H), 4.14 (s, 2H), 2.62 (t, J =
6.01 (m, 1H), 4.20 (s, 2H), 2.69 (d, J = 8.0 Hz, 2H), 2.27-2.22 (m, 2H), 8.0 Hz, 2H), 2.25 (s, 3H), 2.20-2.13 (m, 2H); 13C NMR (100 MHz,
1.27 (s, 9H); 13C NMR (100 MHz, CDCl3) δ: 157.5, 135.8, 135.3, 134.8, CDCl3) δ: 139.0, 138.1, 135.9, 134.8, 134.3, 132.6, 129.1, 128.6,
132.6, 128.5, 128.2, 127.5, 127.2, 126.2, 125.7, 122.9, 59.9, 35.1, 127.5, 127.3, 126.3, 125.8, 125.7, 123.0, 59.9, 27.7, 23.3, 21.1;
31.0, 27.7, 23.3; HRMS (ESI-TOF) m/z: C21H25O2S (M + H)+ calcd for HRMS (ESI-TOF) m/z: C18H19O2S (M + H)+ calcd for 299.1100, found
341.1570, found 341.1575.
299.1106.
4-(((4-Fluorophenyl)sulfonyl)methyl)-1,2-dihydronaphthalene
4-((o-Tolylsulfonyl)methyl)-1,2-dihydronaphthalene (3al): yellow
1
(3ae): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.72-7.69 (m, 2H), oil; H NMR (400 MHz, CDCl3) δ: 7.85 (d, J = 7.6 Hz, 1H), 7.45-7.41
7.20-7.18 (m, 2H), 7.13-7.11 (m, 2H), 7.01 (t, J = 8.8 Hz, 2H), 6.07 (t, (m, 1H), 7.27-7.20 (m, 3H), 7.12-7.06 (m, 3H), 5.90-5.87 (m, 1H),
J = 7.2 Hz, 1H), 4.39 (s, 2H), 3.63 (t, J = 6.8 Hz, 2H), 2.73-2.68 (m, 2H); 4.24 (s, 2H), 2.68-2.63 (m, 5H), 2.23-2.17 (m, 2H); 13C NMR (100
13C NMR (100 MHz, CDCl3) δ: 165.7 (d, J = 254.9 Hz, 1C), 140.2, MHz, CDCl3) δ: 138.4, 136.5, 135.9, 134.7, 133.6, 132.7, 132.4, 130.9,
134.8 (d, J = 3.2 Hz, 1C), 133.9, 131.2 (d, J = 9.6 Hz, 1C), 130.9, 130.5, 127.6, 127.4, 126.4, 126.3, 125.6, 123.1, 59.2, 27.6, 23.3, 20.7;
128.4, 127.9, 127.6, 126.3, 116.2 (d, J = 22.5 Hz, 1C), 57.9, 43.6, 32.5; HRMS (ESI-TOF) m/z: C18H19O2S (M + H)+ calcd for 299.1100, found
19F NMR (282 MHz, CDCl3): : -103.5 (s, 1F); HRMS (ESI-TOF) m/z: 299.1106.
C17H1619FO2S (M + H)+ calcd for 303.0850, found 303.0855.
2-(((3,4-Dihydronaphthalen-1-yl)methyl)sulfonyl)benzonitrile
1
4-(((4-Chlorophenyl)sulfonyl)methyl)-1,2-dihydronaphthalene
(3am): yellow oil; H NMR (400 MHz, CDCl3) δ: 7.91 (d, J = 8.0 Hz,
1
(3af): 73%; yellow oil; H NMR (400 MHz, CDCl3) δ: 7.71 (d, J = 8.4 1H), 7.63-7.54 (m, 3H), 7.13-7.11 (m, 2H), 7.09-7.06 (m, 2H), 6.12-
Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 7.13-7.07 (m, 4H), 5.95-5.93 (m, 1H), 6.09 (m, 1H), 4.67 (m, 2H), 3.71 (t, J = 6.4 Hz, 2H), 2.92-2.87 (m, 2H);
4.23 (s, 2H), 2.69 (t, J = 8.0 Hz, 2H), 2.26-2.21 (m, 2H); 13C NMR (100 13C NMR (100 MHz, CDCl3) δ: 141.0, 139.7, 135.2, 134.9, 133.5,
MHz, CDCl3) δ: 140.3, 136.7, 135.9, 135.1, 132.3, 130.2, 129.0, 127.7, 132.8, 130.8, 129.3, 128.3, 128.3, 127.7, 127.5, 126.3, 115.6, 111.5,
127.5, 126.4, 125.7, 123.0, 60.1, 27.6, 23.3; HRMS (ESI-TOF) m/z: 56.4, 43.7, 32.5; HRMS (ESI-TOF) m/z: C18H16NO2S (M + H)+ calcd for
C17H1635ClO2S (M + H)+ calcd for 319.0554, found 319.0560.
310.0896, found 310.0902.
4-(((4-Bromophenyl)sulfonyl)methyl)-1,2-dihydronaphthalene
4-(((2-Nitrophenyl)sulfonyl)methyl)-1,2-dihydronaphthalene (3an):
(3ag): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.64 (d, J = 8.4 Hz, 2H), yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.84 (d, J = 7.6 Hz, 1H), 7.68-
7.55 (d, J = 8.4 Hz, 2H), 7.15-7.07 (m, 4H), 5.95-5.93 (m, 1H), 4.22 (s, 7.62 (m, 2H), 7.57-7.53 (m, 1H), 7.26-7.24 (m, 2H), 7.17-7.15 (m, 2H),
2H), 2.69 (t, J = 8.0 Hz, 2H), 2.27-2.21 (m, 2H); 13C NMR (100 MHz, 6.16 (t, J = 7.2 Hz, 1H), 4.87 (s, 2H), 3.66 (t, J = 6.4 Hz, 2H), 2.85-2.80
CDCl3) δ: 140.4, 136.7, 135.9, 135.2, 132.3, 130.2, 129.1, 127.8, (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 148.7, 139.9, 134.8, 134.6,
127.6, 126.4, 125.7, 123.1, 60.1, 27.7, 23.3; HRMS (ESI-TOF) m/z: 132.8, 132.6, 132.2, 130.1. 128.8, 128.5, 128.3, 127.7, 126.6, 124.6,
C17H1679BrO2S (M + H)+ calcd for 363.0049, found 363.0054.
57.5, 43.6, 32.5; HRMS (ESI-TOF) m/z: C17H16NO4S (M + H)+ calcd for
4-(((4-(Trifluoromethyl)phenyl)sulfonyl)methyl)-1,2-
330.0795, found 330.0800.
dihydronaphthalene (3ah): yellow solid, mp 84.2-85.4 oC 4-((Mesitylsulfonyl)methyl)-1,2-dihydronaphthalene (3ao): 1H
(uncorrected);1H NMR (400 MHz, CDCl3) δ: 7.91 (d, J = 8.4 Hz, 2H), NMR (400 MHz, CDCl3) δ: 7.24-7.21 (m, 1H), 7.15-7.06 (m, 3H), 6.87
7.65 (d, J = 8.4 Hz, 2H), 7.11-6.99 (m, 4H), 6.01-5.98 (m, 1H), 4.26 (m, (s, 2H), 5.83-5.80 (m, 1H), 4.21 (s, 2H), 2.69 (t, J = 8.0 Hz, 2H), 2.57 (s,
2H), 2.68 (t, J = 8.0 Hz, 2H), 2.27-2.21 (m, 2H); 13C NMR (100 MHz, 6H), 2.27 (s, 3H), 2.23-2.18 (m, 2H); 13C NMR (100 MHz, CDCl3) δ:
CDCl3) δ: 141.7, 135.8, 135.4, 135.1, 132.1, 129.3 (2C), 127.7, 127.6, 143.2, 140.5, 135.9, 134.5, 132.8, 132.3, 131.9, 127.6, 127.3, 126.4,
126.4, 125.8 (t, J = 3.7 Hz, 1C), 125.4, 122.8, 59.9, 27.6, 23.3; 19F 125.8, 123.3, 59.5, 27.6, 23.4, 23.2, 21.0; HRMS (ESI-TOF) m/z:
NMR (282 MHz, CDCl3): : -63.3 (s, 3F); HRMS (ESI-TOF) m/z: C20H23O2S (M + H)+ calcd for 327.1413, found 327.1419.
C18H1619F3O2S (M + H)+ calcd for 353.0818, found 353.0823.
1-(4-(((3,4-Dihydronaphthalen-1
2-(((3,4-Dihydronaphthalen-1-yl)methyl)sulfonyl)naphthalene
(3ap): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 8.36 (s, 1H), 7.89-7.85
yl)methyl)sulfonyl)phenyl)ethanone (3ai): white solid, mp 82.6- (m, 3H), 7.80-7.77(m, 1H), 7.66-7.55 (m, 2H), 7.18-7.17 (m, 1H),
o
1
84.0 C (uncorrected); H NMR (400 MHz, CDCl3) δ: 7.89 (d, J = 8.0 7.02-7.00 (m, 3H), 5.88-5.85 (m, 1H), 4.29 (s, 2H), 2.64 (t, J = 8.0 Hz,
Hz, 2H), 7.80 (d, J = 8.4 Hz, 2H), 7.16-7.15 (m, 2H), 7.12-7.10 (m, 2H), 2H), 2.19-2.13 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 135.8, 135.2,
6.07 (t, J = 7.6 Hz, 1H), 4.42 (s, 2H), 3.64-3.61 (m, 2H), 2.73-2.66 (m, 135.1, 134.9, 132.5, 131.8, 130.5, 129.2, 129.1, 128.9, 127.8, 127.5,
2H), 2.61 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 196.7, 142.4, 140.5, 127.5, 127.3, 126.2, 125.8, 123.3, 123.1, 60.0, 27.6, 23.2; HRMS
140.0, 134.2, 130.1, 129.1, 128.8, 128.5, 128.4, 128.3, 127.5, 126.4, (ESI-TOF) m/z: C21H19O2S (M + H)+ calcd for 335.1100, found
57.7, 43.6, 32.5, 26.9; HRMS (ESI-TOF) m/z: C19H19O3S (M + H)+ calcd 335.1106.
for 327.1049, found 327.1055.
2-(((3,4-Dihydronaphthalen-1-yl)methyl)sulfonyl)thiophene (3aq):
4-(((4-Nitrophenyl)sulfonyl)methyl)-1,2-dihydronaphthalene (3aj): yellow oil; 1H NMR (400 MHz, CDCl3) δ: 7.81-7.78 (m, 2H), 7.11-7.07
o
1
yellow solid, mp 156.8-158.4 C (uncorrected); H NMR (400 MHz, (m, 5H), 5.96-5.93 (m, 1H), 4.23 (s, 2H), 2.72-2.67 (m, 2H), 2.27-2.22
CDCl3) δ: 8.22 (d, J = 8.4 Hz, 2H), 7.97 (d, J = 8.8 Hz, 2H), 7.09-7.08 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 140.3, 139.7, 135.1, 134.7,
(m, 2H), 7.04-7.03 (m, 2H), 6.01-5.99 (m, 1H), 4.30 (m, 2H), 2.68 (t, J 134.3, 134.2, 134.1, 130.5, 128.3, 127.8, 127.6, 126.3, 59.0, 43.6,
= 8.0 Hz, 2H), 2.27-2.22 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 150.7, 32.4; HRMS (ESI-TOF) m/z: C15H15O2S2 (M + H)+ calcd for 291.0508,
143.8, 135.9, 135.6, 132.0, 130.2, 127.9, 127.7, 126.4, 125.3, 123.8, found 291.0513.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 6 of 9
Organic & Biomolecular Chemistry
PAPER
4-((Dodecylsulfonyl)methyl)-1,2-dihydronaphthalene(3at): yellow 4-(((4-chlorophenyl)sulfonyl)methyl)-7-methyl-1,2-
View Article Online
oil; H NMR (400 MHz, CDCl3) δ: 7.35 (d, J = 7.6 Hz, 1H), 7.26-7.15 dihydronaphthalene (3ff): white solid, DOmI:p10.1100339./8C-91O0B40.91321oCK
1
1
(m, 3H), 6.32-6.30 (m, 1H), 4.12 (s, 2H), 2.91 (t, J = 8.0 Hz, 2H), 2.81 (uncorrected); H NMR (400 MHz, CDCl3) δ: 7.71-7.70 (m, 2H), 7.37
(t, J = 8.0 Hz, 2H), 2.41-2.38 (m, 2H), 1.82-1.78 (m, 2H), 1.30-1.24 (m, (d, J = 8.4 Hz, 2H), 6.98 (d, J = 7.6 Hz, 1H), 6.89 (d, J = 8.0 Hz, 2H),
18H), 0.88 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 136.2, 5.85-5.82 (m, 1H), 4.20 (s, 2H), 2.64 (t, J = 8.0 Hz, 2H), 2.28 (s, 3H),
134.7, 132.6, 128.0, 127.8, 126.6, 125.6, 123.1, 56.5, 51.8, 31.9, 2.22-2.17 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 140.3, 137.4, 136.6,
29.6, 29.5, 29.5, 29.3, 29.2, 29.0, 28.4, 27.8, 23.4, 22.7, 21.8, 14.1; 135.8, 133.9, 130.1, 129.6, 129.0, 128.5, 126.9, 125.6, 123.0, 60.1,
HRMS (ESI-TOF) m/z: C23H37O2S (M + H)+ calcd for 377.2509, found 27.7, 23.3, 21.0; HRMS (ESI-TOF) m/z: C18H1835ClO2S (M + H)+ calcd
377.2514.
for 333.0711, found 333.0716.
4-((Ethylsulfonyl)methyl)-1,2-dihydronaphthalene (3au): yellow oil; 7-(tert-butyl)-4-(((4-chlorophenyl)sulfonyl)methyl)-1,2-
1H NMR (400 MHz, CDCl3) δ: 7.36 (d, J = 7.2 Hz, 1H), 7.27-7.16 (m, dihydronaphthalene (3gf): white solid, mp 100.7-102.0 oC
1
3H), 6.33-6.30 (m, 1H), 4.14 (s, 2H), 2.99-2.93 (m, 2H), 2.81 (t, J = (uncorrected); H NMR (400 MHz, CDCl3) δ: 7.69 (d, J = 8.8 Hz, 2H),
8.0 Hz, 2H), 2.41-2.36 (m, 2H), 1.37 (t, J = 7.6 Hz, 3H); 13C NMR (100 7.34 (d, J = 8.8 Hz, 2H), 7.09-7.04 (m, 2H), 6.94 (d, J = 8.0 Hz, 1H),
MHz, CDCl3) δ: 136.1, 134.8, 132.5, 128.0, 127.8, 126.6, 125.5, 123.0, 5.92-5.90 (m, 1H), 4.21 (s, 2H), 2.69 (t, J = 8.0 Hz, 2H), 2.27-2.22 (m,
55.8, 46.0, 27.7, 23.4, 6.2; HRMS (ESI-TOF) m/z: C13H17O2S (M + H)+ 2H), 1.29 (s, 9H); 13C NMR (100 MHz, CDCl3) δ: 150.6, 140.2, 136.7,
calcd for 237.0944, found 237.0949.
135.4, 134.2, 130.2, 129.6, 128.9, 125.5, 124.8, 123.1, 122.7, 60.1,
4-(((4-chlorophenyl)sulfonyl)methyl)-5-methoxy-1,2-
34.4, 31.2, 28.0, 23.4; HRMS (ESI-TOF) m/z: C21H2435ClO2S (M + H)+
dihydronaphthalene (3bf): white solid, mp 98.1-99.3 oC calcd for 375.1180, found 375.1186.
1
(uncorrected); H NMR (400 MHz, CDCl3) δ: 7.54 (d, J = 8.8 Hz, 2H), 4-(((4-Chlorophenyl)sulfonyl)methyl)-7-fluoro-1,2-
7.21 (d, J = 7.6 Hz, 2H), 7.02 (t, J = 8.0 Hz, 1H), 6.70 (d, J = 7.6 Hz, dihydronaphthalene (3hf): white solid, mp 85.0-86.2 oC
1H), 6.45 (d, J = 7.6 Hz, 1H),6.09 (t, J = 5.2 Hz, 1H), 4.69 (s, 2H), 3.64 (uncorrected); 1H NMR (400 MHz, CDCl3) δ: 7.74-7.71 (m, 2H), 7.44-
(s, 3H), 2.58 (t, J = 7.6 Hz, 2H), 2.15-2.10 (m, 2H); 13C NMR (100 MHz, 7.42 (m, 2H), 7.15-7.11 (m, 1H), 6.83-6.78 (m, 2H), 5.86-5.83 (m, 1H),
CDCl3) δ: 155.2, 139.8, 139.2, 137.0, 136.5, 129.9, 128.2, 128.0, 4.21 (s, 2H), 2.68 (t, J = 8.0 Hz, 2H), 2.25-2.20 (m, 2H); 13C NMR (100
125.5, 121.0, 120.3, 109.4, 62.6, 54.9, 28.9, 22.9; HRMS (ESI-TOF) MHz, CDCl3) δ: 161.8 (d, J = 246.2 Hz, 1C), 140.5, 138.5 (d, J = 7.6 Hz,
m/z: C18H1835ClO3S (M + H)+ calcd for 349.0660, found 349.0665.
4-(((4-chlorophenyl)sulfonyl)methyl)-6-methyl-1,2-
1C), 136.5, 134.3 (d, J = 2.1 Hz, 1C), 130.1, 129.1, 128.5, 124.9 (t, J =
6.2 Hz, 1C), 114.8 (d, J = 21.2 Hz, 1C), 112.8 (d, J = 21.2 Hz, 1C), 60.1,
dihydronaphthalene (3cf) and 4-(((4-chlorophenyl)sulfonyl)methyl)- 27.8, 27.8, 23.0; 19F NMR (282 MHz, CDCl3): : -114.1 (s, 1F); HRMS
8-methyl-1,2-dihydronaphthalene (3cf’): yellow solid, mp 111.2- (ESI-TOF) m/z: C17H1535Cl19FO2S (M + H)+ calcd for 337.0460, found
113.5 oC (uncorrected); 1H NMR (400 MHz, CDCl3) δ: 7.70 (d, J = 8.8 337.0465.
Hz, 1.5H), 7.59 (d, J = 8.8 Hz, 0.5H), 7.37 (d, J = 8.4 Hz, 1.5H), 7.27 (d, 7-Chloro-4-(((4-chlorophenyl)sulfonyl)methyl)-1,2-
J = 9.2 Hz, 0.5H), 7.07 (t, J = 7.6 Hz, 0.3H), 7.02-6.95 (m, 2.4H), 6.91 dihydronaphthalene (3if): yellow solid, mp 96.5-98.1 oC
(d, J = 6.0 Hz, 0.3H), 6.03 (t, J = 7.6 Hz, 0.25H), 5.93-5.91 (m, 0.75H), (uncorrected); 1H NMR (400 MHz, CDCl3) δ: 7.74-7.71 (m, 2H), 7.45-
4.37 (s, 0.5H), 4.22 (s, 1.5H), 3.63 (t, J = 6.8 Hz, 0.5H), 2.74-2.68 (m, 7.43 (m, 2H), 7.09 (s, 3H), 5.90-5.88 (m, 1H), 4.20 (s, 2H), 2.67 (t, J =
0.5H), 2.62 (t, J = 8.4 Hz, 1.5H), 2.24-2.19 (m, 4.5H); 13C NMR (100 8.0 Hz, 2H), 2.26-2.20 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 140.6,
MHz, CDCl3) δ: 140.2, 140.0, 137.9, 137.1, 136.7, 135.0, 134.5, 134.2, 137.7, 136.4, 135.4, 132.9, 130.8, 130.1, 129.2, 127.7, 126.4, 125.0,
133.6, 132.1, 130.5, 130.1, 129.8, 129.6, 128.9, 128.9, 128.2, 128.2, 124.5, 59.9, 27.5, 23.0; HRMS (ESI-TOF) m/z: C17H1535Cl2O2S (M + H)+
127.2, 125.8, 125.6, 123.4, 121.1, 60.3, 57.9, 43.6, 32.4, 23.3, 22.9, calcd for 353.0164, found 353.0170.
21.2, 19.7; HRMS (ESI-TOF) m/z: C18H1835ClO2S (M + H)+ calcd for 7-Bromo-4-(((4-chlorophenyl)sulfonyl)methyl)-1,2-
333.0711, found 333.0716.
4-(((4-Chlorophenyl)sulfonyl)methyl)-7-methoxy-1,2-
dihydronaphthalene (3jf): white solid, mp 144.3-145.9 oC
(uncorrected);1H NMR (400 MHz, CDCl3) δ: 7.72 (d, J = 8.4 Hz, 2H),
dihydronaphthalene (3df): yellow solid, mp 88.9-90.7 oC 7.43 (d, J = 8.4 Hz, 2H), 7.26-7.23 (m, 2H), 7.03-7.01 (m, 1H), 5.92-
1
(uncorrected); H NMR (400 MHz, CDCl3) δ: 7.62 (d, J = 8.8 Hz, 2H), 5.91 (m, 1H), 4.19 (s, 2H), 2.67 (t, J = 8.0 Hz, 2H), 2.25-2.19 (m, 2H);
7.32 (d, J = 8.8 Hz, 2H), 7.03 (d, J = 8.8 Hz, 2H), 6.74-6.71 (m, 1H), 13C NMR (100 MHz, CDCl3) δ: 140.7, 138.1, 136.5, 135.7, 131.4,
5.98 (t, J = 7.6 Hz, 1H), 4.35 (s, 2H), 3.78 (s, 3H), 3.62 (d, J = 6.4 Hz, 130.7, 130.2, 129.4, 129.2, 125.1, 124.8, 121.3, 60.0, 27.5, 23.2;
2H), 2.69-2.64 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 159.2, 140.3, HRMS (ESI-TOF) m/z: C17H1579Br35ClO2S (M + H)+ calcd for 396.9659,
137.2, 132.5, 132.3, 130.2, 129.8, 129.8, 129.1, 129.0, 127.5, 113.7, found 396.9665.
58.0, 55.3, 43.7, 32.4; HRMS (ESI-TOF) m/z: C18H1835ClO3S (M + H)+ 4-(((4-chlorophenyl)sulfonyl)methyl)-7-(trifluoromethyl)-1,2-
calcd for 349.0660, found 349.0665.
7-(benzyloxy)-4-(((4-chlorophenyl)sulfonyl)methyl)-1,2-
dihydronaphthalene (3kf): white solid, mp 103.4-134.8 oC
(uncorrected); H NMR (400 MHz, CDCl3) δ: 7.73 (d, J = 8.8 Hz, 2H),
1
1
dihydronaphthalene (3ef): yellow oil; H NMR (400 MHz, CDCl3) δ: 7.42 (d, J = 8.8 Hz, 2H), 7.36 (d, J = 7.6 Hz, 2H), 7.25 (t, J = 7.2 Hz,
7.60 (d, J = 8.8 Hz, 2H), 7.43-7.38 (m, 4H), 7.30 (d, J = 8.4 Hz, 2H), 1H), 6.06-6.03 (m, 1H), 4.23 (s, 2H), 2.76 (t, J = 8.0 Hz, 2H), 2.31-2.26
7.02 (d, J = 8.4 Hz, 2H), 6.78 (d, J = 8.8 Hz, 2H), 5.98 (t, J = 7.2 Hz, (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 140.7, 137.6, 136.5 (d, J = 7.5
1H), 5.03 (s, 2H), 4.34 (s, 2H), 3.60 (d, J = 6.8 Hz, 2H), 2.69-2.64 (m, Hz, 1C), 135.6, 130.1, 129.2, 129.1 (d, J = 32.2 Hz, 1C), 125.1, 124.4
2H); 13C NMR (100 MHz, CDCl3) δ: 158.3, 140.3, 137.2, 136.7, 132.7, (q, J = 3.7 Hz, 1C), 124.0 (d, J = 270.5 Hz, 1C), 123.4 (q, J = 4.0 Hz, 1C),
132.4, 130.2, 129.8, 129.7, 129.1, 128.6, 128.6, 128.0, 127.5, 127.4, 123.3, 122.6, 59.8, 27.4, 23.0; 19F NMR (282 MHz, CDCl3): : -62.6 (s,
114.6, 70.0, 57.9, 43.7, 32.4; HRMS (ESI-TOF) m/z: C24H2235ClO3S (M 3F); HRMS (ESI-TOF) m/z: C18H1535Cl19F3O2S (M + H)+ calcd for
+ H)+ calcd for 425.0973, found 425.0978.
387.0428, found 387.0433.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
Organic & Biomolecular Chemistry
Please do not adjust margins
Organic & Biomolecular Chemistry
PAPER
1-(((4-chlorophenyl)sulfonyl)methyl)-3,4-dihydrophenanthrene
We thank the Scientific Research Fund of Hunan Provincial
View Article Online
DOI: 10.1039/C9OB01321K
(3lf): white solid, mp 86.5-87.7 oC (uncorrected); 1H NMR (400 MHz, Education Department (No. 16A087), Hunan Institute of Science
CDCl3) δ: 8.00 (d, J = 8.4 Hz, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.67 (d, J = and Technology Innovation Foundation For Postgraduate
8.4 Hz, 2H), 7.59 (d, J = 8.4 Hz, 1H), 7.51-7.48 (m, 1H), 7.44 (d, J = (YCX2018A01), Natural Science Foundation of Hunan Province (No.
8.0 Hz, 1H), 7.30-7.28 (m, 3H), 6.00-5.98 (m, 1H), 4.31 (s, 2H), 3.10 2018JJ3208 and 2019JJ50204) and National Natural Science
(t, J = 8.4 Hz, 2H), 2.37-2.31 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: Foundation of China (No. 21602056 and 51874132) for financial
140.3, 136.5, 134.6, 132.9, 131.6, 131.0, 130.1, 129.4, 129.0, 129.0, support.
128.5, 126.2, 126.2, 125.5, 123.5, 121.5, 60.4, 22.9, 22.6; HRMS
(ESI-TOF) m/z: C21H1835ClO2S (M + H)+ calcd for 369.0771, found Notes and references
369.0716.
1
(a) Z.-J. Qiao and X.-F. Jiang, Org. Lett., 2016, 18, 1550; (b) C.
M. Rayner, Contemp. Org. Synth., 1994, 1, 191; (c) A.-N.-R.
Alba, X. Companyó, and R. Rios, Chem. Soc. Rev., 2010, 39,
2018; (d) T. G. Back, K. N. Clary and D.-T. Gao, Chem. Rev.,
2010, 110, 4498; (e) H. Min, G.-H. Xiao, W.-J. Liu and Y. Liang,
Org. Biomol. Chem., 2016, 14, 11088; (f) M. Petrini, Chem.
Rev., 2005, 105, 3949; (g) Jan-E. Bäckvall, R. Chinchilla, C.
Nájera and M. Yus, Chem. Rev., 1998, 98, 2291; (h) M. Wang
and X.-F. Jiang, Top. Curr. Chem., 2018, 376, 14; (i) W.-J. Liu,
H. Min, X.-M. Zhu, G.-B. Deng and Y. Liang, Org. Biomol.
Chem., 2017, 15, 9804.
(a) P. Dang, Z.-L. Zheng and Y. Liang, J. Org. Chem., 2017, 82,
2263; (b) J.-P. Wei, Y.-M. Li and X.-F. Jiang, Org. Lett., 2016,
18, 340; (c) R.-J. Song, Y. Liu, Y.-Y. Liu and J.-H. Li, J. Org.
Chem., 2011, 76, 1001; (d) Z.-J. Qiao and X.-F. Jiang, Org.
Biomol. Chem., 2017, 15, 1942; (e) J. Yang, Y.-Y. Liu, R.-J.
Song, Z.-H. Peng and J.-H. Li, Adv. Synth. Catal., 2016, 358,
2286; (f) Y.-M. Li, M. Wang and X.-F. Jiang, ACS Catal., 2017,
7, 7587; (g) M. Wang, Z.-J. Qiao, J.-Y. Zhao and X.-F. Jiang,
Org. Lett., 2018, 20, 6193; (h) Y.-M. Li, W.-S. Xie and X.-F.
Jiang, Chem. Eur. J., 2015, 21, 16059.
(a) R. L. Lopez de Cornpadre, R. A. Pearlstein, A. J. Hopfinger
and J. K. Seydel, J. Med. Chem., 1987, 30, 900; (b) Y. Tanetani,
K. Kaku, K. Kawai, T. Fujioka and T. Shimizu, Pestic. Biochem.
Physiol., 2009, 95, 47; (c) M. Perez, P.-G. Echeverria, E.
Martinez-Arripe, M. EzZoubir, R. Touati, Z.-G. Zhang, J.-P.
Genet, P. Phansavath, T. Ayad and V. Ratovelomanana-Vidal,
Eur. J. Org. Chem., 2015, 5949; (d) W.-H. Rao, B.-B. Zhan, K.
Chen, P.-X. Ling, Z.-Z. Zhang and B.-F. Shi, Org. Lett., 2015, 17,
3552; (e) C. Wu, L.-H. Lu, A.-Z. Peng, G.-K. Jia, C. Peng, Z. Cao,
Z. Tang, W.-M. He and X. Xu, Green Chem., 2018, 20, 3683; (f)
W.-H. Bao, C. Wu, J.-T. Wang, W. Xia, P. Chen, Z. Tang, X. Xu
and W.-M. He, Org. Biomol. Chem., 2018, 16, 8403; (g) Y.-J.
Xie, X.-G. Chen, Z. Wan, H.-W. Huang, B. Yi and G.-J. Deng,
Green Chem., 2017, 19, 4294; (h) L.-H. Lu, S.-J. Zhou, W.-B.
He, W. Xia, P. Chen, X. Yu, X. Xu and W.-M. He, Org. Biomol.
Chem., 2018, 16, 9064; (i) G.-Z. Li, H. Xie, J.-J. Chen, Y.-J. Guo
and G.-J. Deng, Green Chem., 2017, 19, 4043.
(a) D.-C. Meadows and J. Gervay-Hague, Med. Res. Rev.,
2006, 26, 793; (b) Y. M. Markitanov, V.-M. Timoshenko and Y.-
G. Shenko, Sulfur Chem., 2014, 35, 188; (c) L. Jiang, Y.-G. Li,
J.-F. Zhou, Y.-M. Chuan, H.-L. Li and M.-L. Yuan, Molecules,
2015, 20, 8213; (d) Y.-Y. Fang, Z.-G. Luo and X.-M. Xu, RSC
Adv., 2016, 6, 59661; (e) M. D. McReynolds, J. M. Dougherty
and P. R. Hanson, Chem. Rev., 2004, 104, 2239; (f) N. V. Zyk E.
K. Beloglazkina, M. A. Belova and N. S. Dubinina, Russ. Chem.
Rev., 2003, 72, 769; (g) A. U. Meyer, K. Straková, T. Slanina
and B. König, Chem. Eur. J., 2016, 22, 8694.
5-(((4-chlorophenyl)sulfonyl)methyl)isoquinoline (3mf’): white
o
1
solid, mp 91.9-93.1 C (uncorrected); H NMR (400 MHz, CDCl3) δ:
9.25 (s, 1H), 8.50 (d, J = 6.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.60 (d,
J = 6.0 Hz, 1H), 7.56-7.52 (m, 3H), 7.46 (d, J = 6.4 Hz, 1H), 7.37 (d, J =
8.8 Hz, 2H), 4.79 (s, 2H); 13C NMR (100 MHz, CDCl3) δ: 153.2, 143.8,
140.9, 136.1, 134.7, 134.6, 130.0, 129.5, 129.4, 128.7, 126.6, 123.6,
116.3, 59.0; HRMS (ESI-TOF) m/z: C16H1335ClNO2S (M + H)+ calcd for
318.0350, found 318.0356.
5-(((4-chlorophenyl)sulfonyl)methyl)-7,8-dihydroquinoline (3nf):
yellow oil; 1H NMR (400 MHz, CDCl3) δ: 8.32-8.30 (m, 1H), 7.74 (d, J
= 8.4 Hz, 2H), 7.49-7.45 (m, 3H), 7.09-7.06 (m, 1H), 5.92-5.90 (m,
1H), 4.19 (s, 2H), 2.93 (t, J = 7.6 Hz, 2H), 2.42-2.37 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ: 156.6, 147.5, 140.7, 136.3, 136.2, 130.1, 130.1,
129.3, 127.9, 124.4, 121.6, 59.5, 30.1, 23.1; HRMS (ESI-TOF) m/z:
C16H1535ClNO2S (M + H)+ calcd for 320.0507, found 320.0512.
5-(((4-chlorophenyl)sulfonyl)methyl)-7,8-dihydroquinoline (3nf):
yellow oil; 1H NMR (400 MHz, CDCl3) δ: 8.32-8.30 (m, 1H), 7.74 (d, J
= 8.4 Hz, 2H), 7.49-7.45 (m, 3H), 7.09-7.06 (m, 1H), 5.92-5.90 (m,
1H), 4.19 (s, 2H), 2.93 (t, J = 7.6 Hz, 2H), 2.42-2.37 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ: 156.6, 147.5, 140.7, 136.3, 136.2, 130.1, 130.1,
129.3, 127.9, 124.4, 121.6, 59.5, 30.1, 23.1; HRMS (ESI-TOF) m/z:
C16H1535ClNO2S (M + H)+ calcd for 320.0507, found 320.0512.
7-(((4-Chlorophenyl)sulfonyl)methyl)-4,5-
dihydrobenzo[b]thiophene (3pf): yellow solid, mp 69.4-71.2oC
(uncorrected);1H NMR (400 MHz, CDCl3) δ: 7.73 (d, J = 8.4 Hz, 2H),
7.39 (d, J = 8.8 Hz, 2H), 7.09 (s, 2H), 5.90-5.88 (m, 1H), 4.20 (s, 2H),
2.67 (t, J = 8.0 Hz, 2H), 2.26-2.20 (m, 2H); 13C NMR (100 MHz, CDCl3)
δ: 143.7, 140.7, 137.1, 131.9, 130.1, 1293, 127.5, 124.8, 124.3,
124.2, 58.2, 43.4, 32.3; HRMS (ESI-TOF) m/z: C15H1435ClO2S2 (M + H)+
calcd for 325.0118, found 325.0124.
(2-(phenylsulfonyl)ethene-1,1-diyl)dibenzene (4): white oil; 1H
NMR (400 MHz, CDCl3) δ: 7.48 (d, J = 8.0 Hz, 2H), 7.36 (t, J = 7.6 Hz,
1H), 7.27-7.15 (m, 8H), 7.09 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 7.2 Hz,
2H), 6.93 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 155.3, 141.4, 139.1,
135.5, 133.0, 130.4, 129.8, 129.0, 128.8, 128.7, 128.3, 128.3, 127.9,
127.6; HRMS (ESI-TOF) m/z: C20H17O2S (M + H)+ calcd for 321.0944,
found 321.0949.
2
3
4
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
5
(a) P. Katrun, C. Mueangkaew, M. Pohmakotr, V. Reutrakul, T.
Jaipetch, D. Soorukram and C. Kuhakarn, J. Org. Chem., 2014,
79, 1778; (b) F. Han, B. Su, P. Song, Y. Wang, L. Jia, S. Xun, M.
Hu and L. Zou, Tetrahedron, 2018, 74, 5908; (c) S. C. Cullen, S.
Shekhar and N. K. Nere, J. Org. Chem., 2013, 78, 12194; (d)
L.-Y. Xie, S. Peng, F. Liu, G.-R. Chen, W. Xia, X.-Y. Yu, W.-F. Li,
Z. Cao and W.-M. He, Org. Chem. Front., 2018, 5, 2604; (e) F.-
H. Xiao, C. Liu, S.-S. Yuan, H.-W. Huang and G.-J. Deng, J. Org.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 8 of 9
Organic & Biomolecular Chemistry
PAPER
Chem., 2018, 83, 10420; (f) M. J. Cabrera-Afonso, Z. P. Lu, C.
B. Kelly, S. B. Lang, R. Dykstra, O. Gutierrez and G. A.
Molander, Chem. Sci., 2018, 9, 3186; (g) L. Cao, J.-X. Li, H.-Q.
Wu, K. Jiang, Z.-F. Hao, S.-H. Luo and Z.-Y. Wang, ACS
Sustainable Chem. Eng., 2018, 6, 4147; (h) Y.-W. Li, T. Liu, G.-
Y.-S. Qiu, and J. Wu, Adv. Synth. Catal., 2019, 361, 1154; (i) J.-
I. Fukuda, K. Nogi and H. Yorimitsu, Asian. J. Org. Chem.,
2017, 8, 2049.
(a) W. Wei, H.-H. Cui, D.-S. Yang, H.-L. Yue, C.-L. He, Y.-L.
Zhang and H. Wang, Green Chem., 2017, 19, 5608; (b) K.
Muralirajan, R. Kancherla and M. Rueping, Angew. Chem. Int.
Ed., 2018, 57, 14787; (c) L.-L. Mao, D.-G. Zheng, X.-H. Zhu, A.-
X. Zhou and S.-D. Yang, Org. Chem. Front., 2018, 5, 232; (d)
A. Sasmal, J. K. Bera, H. Doucet and J. F. Soulé, Eur. J. Org.
Chem., 2018, 44, 6114; (e) J. Wei, J.-X. Jiang, X.-S. Xiao, D.-G.
Lin, Y.-F. Deng, Z.-F. Ke, H.-F. Jiang and W. Zeng, J. Org.
Chem., 2016, 81, 946; (f) B. Ramesh and M. Jeganmohan,
Org. Lett., 2017, 19, 6000.
(a) Y. Liu, Q.-L. Wang, B.-Q. Xiong, P.-L. Zhang, C.-A. Yang, Y.-
X. Gong, J. Liao and K.-W. Tang, Synlett, 2018, 29, 2396; (b)
T.-F. Niu, J. Cheng, C.-L. Zhuo, D.-Y. Jiang, X.-G. Shu and B.-Q.
Ni, Tetrahedron Lett., 2017, 58, 3667; (c) Z.-Y. Wu, H.-Y. Song,
X.-L. Cui, C. Pi, W.-W. Du and Y.-J. Wu, Org. Lett., 2013, 15,
1270; (d) P. Santosh K, S. Paria and O. Reiser, Org. Lett., 2016,
18, 2106; (e) S. K. Pagire, A. Hossain and O. Reiser, Org. Lett.,
2018, 20, 648; (f) H.-J. Qiao, S.-Y. Sun, F. Yang, Y. Zhu, W.-G.
Zhu, Y.-X. Dong, Y.-S. Wu, X.-T. Kong, L. Jiang and Y.-J. Wu,
Org. Lett., 2015, 17, 6086.
(a) K. Zeitler, Angew. Chem. Int. Ed., 2009, 48, 9785; (b) J.
Xuan and W.-J. Xiao, Angew. Chem. Int. Ed., 2012, 51, 6828;
(c) Q.-Q. Zhou, Y.-Q. Zou, L.-Q. Lu, and W.-J. Xiao, Angew.
Chem. Int. Ed., 2019, 58, 1586; (d) J.-R. Chen, X.-Q. Hu, L.-Q.
Lu and W.-J. Xiao, Acc. Chem. Res., 2016, 49, 1911; (e) D. P.
Hari and B. König, Angew. Chem. Int. Ed., 2013, 52, 4734; (f)
W. Ding, L.-Q. Lu, Q.-Q. Zhou, Y. Wei, J.-R. Chen and W.-J.
Xiao, J. Am. Chem. Soc., 2017, 139, 63; (g) H. Wang, Q. Xu, S.
Shen and S.-Y. Yu, J. Org. Chem., 2017, 82, 770; (h) J.-M.-R.
Narayanam and C.-R.-J. Stephenson, Chem. Soc. Rev., 2011,
40, 102; (i) J. Xuan, Z.-G. Zhang and W.-J. Xiao, Angew. Chem.
Int. Ed., 2015, 54, 15632.
View Article Online
DOI: 10.1039/C9OB01321K
6
7
8
9
J. Li, J.-Z. Chen, W. Jiao, G.-Q. Wang, Y. Li, X. Cheng and G.-G.
Li, J. Org. Chem., 2016, 81, 9992.
10 (a) Q.-L. Wang, Z. Chen, Q. Zhou, C.-S. Zhou, B.-Q. Xiong, P.-L.
Zhang, C.-A. Yang and K.-W. Tang, Adv. Synth. Catal., 2019,
361, 2315; (b) Y. Liu, Q.-L. Wang, Z. Chen, Q. Zhou, C.-S. Zhou,
B.-Q. Xiong, P.-L. Zhang, C.-A. Yang and K.-W. Tang, Org.
Biomol. Chem., 2019, 17, 1365; (c) Y. Liu, Q.-L. Wang, Z. Chen,
Q. Zhou, H. Li, C.-S. Zhou, B.-Q. Xiong, P.-L. Zhang and K.-W.
Tang, J. Org. Chem., 2019, 84, 2829; (d) Y. Liu, Q.-L. Wang, C.-
S. Zhou, B.-Q. Xiong, P.-L. Zhang, S.-J. Kang, C.-A. Yang and K.-
W. Tang, Tetrahedron Lett., 2018, 59, 2038; (e) Q.-L. Wang, Z.
Chen, C.-S. Zhou, B.-Q. Xiong, P.-L. Zhang, C.-A. Yang, Y. Liu
and K.-W. Tang, Tetrahedron Lett., 2018, 59, 4551; (f) Y. Liu,
Q.-L. Wang, C.-S. Zhou, B.-Q. Xiong, P.-L. Zhang, S.-J. Kang, C.-
A. Yang and K.-W. Tang, J. Org. Chem., 2018, 83, 2210; (g) Y.
Liu, J.-L. Zhang, R.-J. Song and J.-H. Li, Org. Chem. Front.,
2014, 1, 1289; (h) Y. Liu, J.-L. Zhang, R.-J. Song and J.-H. Li,
Eur. J. Org. Chem., 2014, 2014, 1177; (i) J.-L. Zhang, Y. Liu, R.-
J. Song and J.-H. Li, Synlett., 2014, 25, 1031.
11 M. A. Cismesia and T. P. Yoon, Chem. Sci., 2015, 6, 5426.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C9OB01321K
Table of Contents
Visible-light-mediated C−C σ–bond sulfonylation/arylation of vinylcyclopropanes with sulfonyl chlorides for the
synthesis of 1-sulfonylmethyl-3,4-dihydronaphthalenes
Qiao-Lin Wang,† Wen-Zheng Zhang,† Quan-Zhou, Cong-Shan Zhou, Bi-QuanXiong, Ke-Wen Tang, Yu Liu*
Ru(bpy)3Cl2 (5 mol%)
2,6-lutidine (2 equiv)
R1
O
O
S
O
1,4-dioxane (2 mL)
R2
S
Cl
R2
R1
+
5 W blue LED light
O
Ar, 24 h, 100 oC
visible-light-catalysis
good functional group tolerance
readily available substrates
33 examples up to 91% yield
An efficient visible-light-mediated sulfonylation/arylation of C−C σ–bond in vinylcyclopropanes with sulfonyl chlorides
to synthesize 1-sulfonylmethyl-substituted 3,4-dihydronaphalenes is developed.