Base-controlled divergent synthesis of vinyl sulfones from (benzylsulfonyl)benzenes and paraformaldehyde

Article abstract of DOI:10.1039/d0ob00362j

A tuneable metal-free protocol for the selective preparation of a-substituted vinyl sulfone and (E)-vinyl sulfone derivatives has been described. In this process, stable paraformaldehyde was used as the carbon source. The base played an important role in the selectivity control of transformations. More than 50 products were synthesized with excellent chemoselectivity and broad functional group tolerance.

Full text of DOI:10.1039/d0ob00362j

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DOI: 10.1039/D0OB00362J
ARTICLE
Base-controlled divergent synthesis of vinyl sulfones from
(benzylsulfonyl)benzenes and paraformaldehyde
Received 00th January 20xx,
Accepted 00th January 20xx
Fuhong Xiao,* Yangling Hu, Huawen Huang, Fen Xu,* and Guo-Jun Deng
DOI: 10.1039/x0xx00000x
A tuneable metal-free protocol for the selective preparation of α-substituted vinyl sulfone and (E)-vinyl sulfone
derivatives has been described. In this process, stable paraformaldehyde was used as the carbon source. The base
played an important role in the selectivity control of transformation. More than 50 products were synthesized with
excellent chemoselectivity and broad functional group tolerance.
In 2017, Lei described a transition-metal-free, visible light-
mediated Markovnikov addition of sulfinic acids to terminal
alkynes via α-vinyl radical/sulfonyl radical cross coupling.15 In
Introduction
Divergent synthesis has garnered increasing attention
because complex molecules can be constructed from available
raw materials. The improvement of chemoselectivity and
regioselectivity in divergent synthesis has always been a key
challenge in modern synthetic chemistry.1 Recent studies
mainly focused on selective control by the use of catalysts,2
ligands3 or solvents.4 Particularly, studies on the base-
controlled chemoselectivity and regioselectivity have attracted
much attention and intensive studies were conducted to
explore reaction flexibility.5
Vinyl sulfones as significant sulfur-containing compounds
are widely found in bioactive molecules.6 They played an
important role in the area of synthetic organic chemistry
owing to the prevalent molecular skeleton for various organic
transformations.7 Therefore, considerable effort has been
devoted to the development of conventional approaches for
the synthesis of vinyl sulfones.8 The direct cross-coupling of
sulfonyl derivatives with alkene or alkyne sources has emerged
to be an efficient protocol. Generally, the facile sulfonyl
sources could be originated from sodium sulfinate,9 sulfonyl
hydrazide,10 sulfinic acid,11 thiols,12 and so on13.The most
popular method has been developed for the synthesis of (E)-
vinyl sulfones, without obtaining divergent products, such as
α-substituted vinyl sulfones. However, the synthesis of α-
substituted vinyl sulfones remains a major challenge. For
example, in 2013, Shi reported a gold-catalyzed Markovnikov
addition of sulfinic acids to alkynes for the synthesis of α-
substituted vinyl sulfones with an exclusive regioselectivity.14
this text, our goal is dedicated to seek the divergent and
selective method for the synthesis of vinyl sulfones, including
(E)-vinyl sulfones and α-substituted vinyl sulfones. In recent
years, great progress has been made in using
paraformaldehyde as a one-carbon source to construct
complex skeletons.16 With the respect to our recent studies on
the paraformaldehyde insertion to construct heterocycles,17
herein, we describe a base-controlled protocol for the
preparation of (E)-vinyl sulfones via 1,2-sulfonyl migration
strategy and α-substituted vinyl sulfones through direct
alkenylation of (benzylsulfonyl)benzenes.
O O
S
N
Et3
Ar2
Ar1
base
controled
Ar2
S
O O
Ar2
(CH2O)n
Ar1
pyridin
S
O O
Ar1
e
Scheme 1 Base controlled preparation of α-substituted vinyl
sulfones and (E)-vinyl sulfones.
Results and discussion
We chose the reaction of (benzylsulfonyl)benzene (1a) and
paraformaldehyde as a model reaction (Table 1). Base was
controlled in this reaction as it can play an important role in
the transformation. The (E)-vinyl sulfone product 2a was
generated as a major product when ethylenediamine,
tributylamine and Et3N were used as the base (entries 1-3).
And it was found that Et3N was the best base, affording 2a in
78% yield. Other solvents such as DMSO, DMAc and NMP gave
2a in lower yields (entries 4-6). Both the reaction yield and the
selectivity of 2a were further improved when 0.8 equiv. of Et3N
was used (entry 7). Interestingly, another isomer of product 3a
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry
of Education, Key Laboratory for Green Organic Synthesis and Application of
Hunan. Province, College of Chemistry, Xiangtan University, Xiangtan 411105,
China. e-mail: fhxiao@xtu.edu.cn; xufen@xtu.edu.cn;
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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was obtained as a major product when the inorganic base such different functional groups, such as alkyl, halides and
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as K2CO3, KHCO3, and K3PO4 were used (entries 8-10). A higher trifluoromethyl at the para-position of DtOheI: 1p0.h10e3n9y/lD0riOnBg00w3e6r2eJ
yield of 3a was obtained when the morpholine was used (entry viable coupling partners, delivering the desired olefins 2l−2r in
11). A further higher yield could be obtained using pyridine as 38−85% yields. Sulfones containing a naphthyl or quinolyl
the base (entry 12). The yield of 3a was improved to 79% by moeities, were also participated in this rearrangement
reducing the amount of paraformaldehyde and decreasing the reaction (2t−2v).
o
reaction temperature to 120 C (entry 14). Delightedly, both
Table 2 Substrate scope for the synthesis of (E)-vinyl sulfones a
the reaction yield and regioselectivity of the product 3a was
O
O
increased by increasing the amount of DMF solvent (entry 15).
Moreover, the desired product was not observed when the
reaction was carried out in the absence of paraformaldehyde
(entry 16). No desired products were obtained when
benzaldehyde or 1-octanal were used as substrates.
R2
S
Et3N
C
R1
S
H
R2
R1
(HCHO)n
+
DMF, 140 o
C
O
O
1
2
, R1 = H, 83%
2a
, R1 = 4-CH3, 69%
, R1 = 4-Cl, 82%
2b
2d
2f
, R1 = 4-F, 85%
2c
2e
O
O
, R1 = 4-Br, 65%
, R1 = 4-CF3, 30%
S
Table 1. Optimization of reaction conditionsa
C
H
1 = 4-OCF3, 37%
, R1 = 3-CH3, 56%
, R1 = 2-F, 87%
R1
2g
2h
2j
R
, R1 = 2-CN, 22%
2i
O
O
Ph
Ph
base
, R1 = 2-CH3, trace
2k
Ph
S
S
(HCHO)n
+
Ph
S
O
C
Ph
Ph
O
O
O
solvent
, R2 = 4-CH3, 38%
, R2 = 4-Et, 49%
H
O
O
2l
2m
2o
S
, R2 = 4-t-Bu, 78%
, R2 = 4-F, 74%
, R2 = 4-Br, 74%
, R2 = 2-CH3, trace
2n
2p
2r
1a
2a
3a
C
R2
, R2 = 4-Cl, 69%
, R2 = 4-CF3, 85%
H
2q
2s
Yieldb(%)
Entry
Base
Solvent
O
O
O
O
S
2a
3a
N
S
C
H
C
H
1
2
3
4
ethylenediamine
tributylamine
Et3N
DMF
DMF
DMF
DMSO
DMAc
NMP
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
44
61
78
62
71
58
86
9
8
7
15
9
5
6
R
2t
, R = H, 56%
2v
, 23%
2u
, R = Cl, 48%
Et3N
Et3N
Et3N
Et3N
K2CO3
KHCO3
K3PO4
morpholine
pyridine
pyridine
pyridine
pyridine
Et3N
aConditions: 1 (0.2 mmol), (HCHO)n (1.8 mmol), DMF (0.4 mL),
5
o
o
140 C, Et3N (0.8 equiv.), 140 C, 18 h, under Ar. Isolated yield
6
7c
8
based on 1.
5
29
24
33
42
55
60
79
89
0
Table 3 Substrate scope for the synthesis of α-substituted vinyl
sulfonesa
9
7
6
10
11
12
13d
14d, e
15d, e, f
16g
R2
R2
30
16
12
13
4
pyridine
S
O
S
+
(HCHO)n
R1
R1
O
DMF, 120 o
C
O
O
1
3
, R1 = 4-H, 86%
, R1 = 4-CH3, 75%
, R1 = 4-Cl, 80%
, R1 = 4-Br, 70%
, R1 = 4-NO2, 45%
, R1 = 3-CH3, 82%
3g
, R1 = 2-F, 85%
, R1 = 2-CN, 49%
, R1 = 2,6-Cl, 87%
3a
3b
3f
, R1 = 2-CH3, 87%
0
3c
3d
3e
3h
3i
S
O
R1
O
aConditions: 1a (0.2 mmol), (HCHO)n (1.8 mmol), base (1 equiv.),
solvent (0.4 mL), 140 oC, 18 h, under Ar. DMF =N,N-
dimethylformamide, DMAc = N,N-dimethylacetamide, NMP =N-
methyl pyrrolidone. b Yield based on 1a and dodecane as an internal
standard. c Et3N(0.8 equiv). d Under air. e (HCHO)n (1 mmol), pyridine
(1.0 equiv), 120 oC, 18 h. f DMF (1 mL). g Without (HCHO)n.
3j
, R2 = 4-Et , 83%
, R2 = 4-Cl, 69%
3k
3l
3n
3o
, R2 = 4- tBu, 86%
, R2 = 4-Br, 74 %
R2
3m, R2 = 4-F, 83%
3p, R2 = 4-CF3, 72%
S
O
O
R
Ph
S
Ph
O
O
S
Ph
S
With the optimal reaction conditions in hand, we next
investigated the substrate scope for the synthesis of (E)-vinyl
sulfones. The results are listed in Table 2. First, the effect of
functional groups attached on the benzyl ring (R1) was
examined. Moderate to good yields were obtained when
methyl (2b) and halides (2c–2e) were present at the para
position on benzyl ring. The electronic effect of the
substituents was significant since substrates with
trifluoromethyl (2f) and trifluoromethoxy (2g) groups gave
lower yields. However, the steric effect of the substituents on
the yields was elusive (p-Me 69% vs o-Me trace and p-F 85% vs
b
3s
, R = CH3, 74%
O
O
O
O
b
3t
, R = Et, 72%
b
3q
3r
, 52%
, 62 %
3u
, R = cyclopropyl, 79%
N
Ph
S
O
S
O O
Ph
S
O
O
O
3v
3w
3x
, 30%
, 61%
, 50%
aConditions: 1 (0.2 mmol), (HCHO)n (1 mmol), pyridine (0.2
mmol), DMF(1 mL), 120 C,18 h, under air. KI (30% mmol)
was added.
o
b
We next sought to expand the substrate scope for the
o-F 87%). Subsequently,
a
range of substituted
synthesis of α-substituted vinyl sulfones (Table 3). Again, the
benzylarylsulfones were evaluated. Benzylarylsulfones with
2 | J. Name., 2012, 00, 1-3
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ARTICLE
effect of the substituent attached on the benzyl ring (R1) was 2). Thus, conjugate Michael addition of aliphatViciewsAercticolenOdnalirnye
examined. The model reaction of (benzylsulfonyl)benzene (1a) amines to vinyl sulfone afforded the corrDeOspI:o10n.d10in39g/Dpr0oOdBu0c0t3s62inJ
with paraformaldehyde gave the desired product 3a in 86% good yields. Simple cyclic secondary amines, such as piperidine
isolated yield. Other substrates with methyl, chloro and bromo (4a), morpholine (4b), thiomorpholine (4c), 1-methylpiperazine
groups at the para position reacted with paraformaldehyde (4d) and piperidin-4-one (4e) proceeded smoothly. Chain
smoothly to give the corresponding α-substituted vinyl secondary amine (4f) was well tolerated in the present system,
sulfones (3b–3d) in good yields. While the substrates with p- the product 5f was isolated in 77% yield. Furthermore, this
NO2 (1e) and o-CN (1i) groups showed modest reactivity to reaction system could also be applied to the direct
give in lower yields. Steric effect on the benzyl ring has no sulfenylation of (1-(phenylsulfonyl)vinyl)benzene with p-
obvious impact on this α‑methylenation reaction since o-Me thiocresol (4h). It is noteworthy that CH3OH and DMSO
(1g),
m-Me
(1f),
and
p-Me
(1b)
substituted (Pummerer reaction) were also proved to be suitable coupling
with (benzylsulfonyl)benzene (1a) and
(benzylsulfonyl)benzenes afforded in similar yields (75–87%) partners
for corresponding products of 3g, 3f, and 3b, respectively. paraformaldehyde to construct C-O and C-S bonds,
Benzyl ring bearing 2,6-dichloro substituents (1j) was also respectively.
suitable unit, giving the desired product (3j) in 87% yield. A
To understand the mechanism of the reaction, control
series of benzylarylsulfones (1k–1q) were also tested (R2). The
experiments under modified conditions were performed
para-substituted
benzylarylsulfones
possessing
either
(Scheme 3). No desired product was observed in absence of
Et3N when (1-(phenylsulfonyl)vinyl)benzene 3a was used as a
substrate (Scheme 3, a), while the rearrangement product 2a
was detected when the reaction was carried out under
electron-donating (1k and 1l) or electron-withdrawing (1m–1p)
groups on the aromatic ring were successfully employed for
the reaction to give the corresponding products (3k–3p) in
good yields. When the benzyl or phenyl ring was replaced by
naphthyl (1q, 1r and 1v) or quinolyl (1w) groups, the reaction
afforded the desired products in moderate yields.
Benzylalkylsulfones (1s–1u) also underwent the methylenation
to give products in good yields when KI was added. Treatment
of dibenzyl sulfone gave dimethylenation product (3x) in 30%
yield.
standard
conditions
(Scheme
3,
b).
(E)-(2-
(Phenylsulfonyl)vinyl)benzene 2a was observed in 28% yield
when the reaction of ethynylbenzene (6a) and sodium
benzenesulfinate (7a) was carried out under the standard
reaction conditions (Scheme 3, c). Two different corresponding
products (2a and 2o) were obtained when (1-
(phenylsulfonyl)vinyl)benzene
3a
and
sodium
4-
Nu
fluorobenzenesulfinate 7a' were used for cross-reaction in one
pot (Scheme 3, d). This result indicates that the reaction for
the formation of (E)-vinyl sulfones from α-vinyl sulfones did
not proceed through an intramolecular migration process.
Reaction conditions
NuH
+
S
S
O
O
O
O
3a
4
5
O O
S
a
5a
5b
5c
5d
, X = CH2, 73%
S
O O
O
(a)
O
S
O
N
X
N
a
DMF, 140 oC, Ar
, X = O, 72%
S
a
, X = S, 75%
Ph
5e
Ph
O
O
X = NCH3, 92%a
a
,
, 60%
3a
2a
, 0%
, 0.2 mmol
O
O
S
O
N
N
S
S
S
O O
S
Ph
5f
Ph
5g
Ph
O
O
O
Et3N (0.8 equiv)
DMF, 140 oC, Ar
S
O O
a
a
b
5h
, 77%
, 86%
, 86%
(b)
(c)
3a
2a
, 85%
, 0.2 mmol
H3CO
H3CS
c
d
S
S
O
S
O
O O
S
O
O
O
O
Et3N (x equiv)
DMSO
CH3OH
PhSO2Na
+
Ph
Ph
Ph
5i
5j
, 71%
, 71%
1l
DMF, 140 oC, Ar
6a
7a
2a,
2a,
x = 0.8;
28%
0%
Scheme 2. Application of present work. Reaction conditions:
(a) 3a (0.2 mmol), 4 (0.4 mmol), Et3N (1.0 equiv), CH3CN (0.8
0.2 mmol
0.4 mmol
x = 0;
o
SO2Na
mL), 90 C, 12 h, under air. (b) 3a (0.2 mmol), 4 (0.4 mmol),
Et3N (1.0 equiv), DMF (1.0 mL), 120 oC, 14 h, under air. Isolated
Ph
Et3N (x equiv)
+
Ph
S
+
2a
2o
(d)
yield based on 3a. (c) 1l (0.2 mmol), (HCHO)n (1 mmol), t-BuOK
(1.0 equiv), CH3OH (0.8 mL), 70 C, 12 h, under air. (d) 1l (0.2
O O
DMF, 140 oC, Ar
o
F
mmol), (HCHO)n (1.2 mmol), Et3N (1.5 equiv), Ac2O(2 equiv),
2o
2o
2a
(35%)
(0%)
x = 0.8;
x = 0;
(28%),
2a
(0%),
DMSO (1.5 mL), 140 oC, 14 h, under Ar.
3a
, 0.2 mmol
7a'
Scheme 3. Control experiments.
Based on the aforementioned experimental results, a
possible reaction mechanism is reasonably proposed (Scheme
4). Initially, (benzylsulfonyl)benzene is gradually deprotonated
Further transformations of selected α-substituted vinyl
sulfones obtained highlight their synthetic usefulness (Scheme
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J. Name., 2013, 00, 1-3 | 3
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to generate the carbanion species A. Then formaldehyde is washed with saturated sodium chloride solution(5 mL). The residue
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DOI: 10.1039/D0OB00362J
attacked by the carbanion species A to obtain intermediate B, was purified by column chromatography on silica (petroleum
which in turn eliminates one molecule of water to form the ether/ethyl acetate = 80:1) to yield the desired product 2a as white
product 3a. Subsequently, the α-vinyl sulfone product 3a solid ( 40.5 mg, 83 %).
undergoes an elimination reaction to form the corresponding
Experimental procedure for the synthesis of 3a: A flat
phenylacetylene and benzenesulfinate intermediate.18 Finally,
bottom reaction tube (10 mL) equipped with a stir bar was charged
the
addition
reaction
of
phenylacetylene
with
with paraformaldehyde (1 mmol, 30 mg), pyridine(0.2 mmol, 16 μL),
benzenesulfinate intermediate to generate the (E)-vinyl
sulfone product 2a.
(benzylsulfonyl)benzene (0.2 mmol, 46.4 mg), and DMF (1 mL)
o
under air. The sealed reaction vessel was stirred at 120 C for 18 h.
H
OH
H
After cooling to room temperature, the reaction was diluted with
ethyl acetate (10 mL). The residue was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate = 10:1)
to yield the desired product 3a as white solid (41.9 mg, 86%).
Ph
O
H
Ph
base
Ph
S
Ph
S
Ph
S
Ph
base-H
O O
O O
O O
base-H
A
B
1a
Analytical data for products
-H2O
Ph
(E)-(2-(phenylsulfonyl)vinyl)benzene (2a)[19]. White solid,
yield 83 %, 40.5 mg, mp 69-70 oC. 1H NMR (400 MHz, CDCl3) δ 7.95
(d, J = 7.2 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.63 – 7.59 (m, 1H), 7.56
– 7.52 (m, 2H), 7.47 – 7.46 (m, 2H), 7.39 – 7.37 (m, 3H), 6.88 (d, J =
15.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.4, 140.5, 133.3, 132.1,
131.1, 129.2, 129.0, 128.5, 127.5, 127.0.
-
Ph SO2
O O
S
base Ph
base-H
S
+
Ph
Ph
O O
Ph
base-H
2a
3a
Scheme 4 Possible reaction mechanism.
(E)-1-Methyl-4-[2-(phenylsulfonyl)vinyl]benzene (2b)[20]
.
White solid, yield 69 %, 35.6 mg, mp 131-132 oC. 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J = 8.0 Hz, 2H), 7.69 – 7.52 (m, 4H), 7.38 (d, J = 7.6
Hz, 2H), 7.20 (d, J = 7.6 Hz, 2H), 6.81 (d, J = 15.4 Hz, 1H), 2.37 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 142.6, 141.8, 140.9, 133.2, 129.8, 129.7,
129.3, 128.6, 127.6, 126.0, 21.5.
Conclusions
In conclusion, we have developed a simple and efficient
base-controlled protocol for the synthesis of vinyl sulfones
from (benzylsulfonyl)benzenes and paraformaldehyde. In this
process, stable paraformaldehyde was used as the carbon
source. Functional groups such as halogen, nitro and cyano
were well tolerated under the optimized reaction conditions.
In this process, the formation of (E)-vinyl sulfones is realized
through a 1,2-sulfonyl migration, and α-substituted vinyl
sulfones via a direct alkenylation of (benzylsulfonyl)benzenes.
(E)-1-Fluoro-4-[2-(phenylsulfonyl)vinyl]benzene (2c)[20]
.
o
1
White solid, yield 85%, 44.6 mg, mp 92-93 C. H NMR (400 MHz,
CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7.68 – 7.62 (m, 2H), 7.56 (t, J = 7.4
Hz, 2H), 7.51 – 7.47 (m, 2H), 7.09 (t, J = 8.4 Hz, 2H), 6.80 (d, J = 15.4
Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 164.3(d, J = 251.5 Hz), 141.1,
140.5, 133.4, 130.6(d, J = 87.1 Hz), 129.4, 128.5(d, J = 3.3 Hz), 127.6,
127.0(d, J = 1.9 Hz), 116.3(d, J = 21.9 Hz). 19F NMR (376 MHz, CDCl3)
δ -107.7.
Experimental
(E)-1-Chloro-4-[2-(phenylsulfonyl)vinyl]benzene (2d)[20]
.
White solid, yield 82%, 47.1 mg, mp 128-130 oC. 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J = 7.0 Hz, 2H), 7.67 – 7.62 (m, 2H), 7.56 (t, J = 7.4
Hz, 2H), 7.43 – 7.36 (m, 4H), 6.84 (d, J = 15.4 Hz, 1H). 13C NMR (100
MHz, CDCl3) δ 141.0, 140.5, 137.3, 133.5, 130.8, 129.7, 129.4, 129.4,
127.9, 127.7.
General information
All isolated compounds were characterized on H NMR , 13C NMR
1
and 19F NMR spectra recorded on Bruker-AV (400 , 100 , 376 MHz,
respectively) instrument internally referenced to tetramethylsilane
(TMS) or chloroform signals. Mass spectra were measured on
Agilent 5975 GC-MS instrument (EI). High-resolution mass spectra
were recorded at the Keeloud (shanghai) Biotechnology co. LTD.
HRMS was conducted using electrospraying ionization (ESI) and was
performed on a Thermo Scientific LTQ Orbitrap XL. All melting
points were measured with the samples after column
chromatography and uncorrected. Column chromatography was
performed on silica gel.
(E)-1-Bromo-4-[2-(phenylsulfonyl)vinyl]benzene (2e)[20]
.
White solid, yield 82%, 47.1 mg, mp 128-130 oC. 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J = 7.0 Hz, 2H), 7.67 – 7.62 (m, 2H), 7.56 (t, J = 7.4
Hz, 2H), 7.43 – 7.36 (m, 4H), 6.84 (d, J = 15.4 Hz, 1H). 13C NMR (100
MHz, CDCl3) δ 141.0, 140.5, 137.3, 133.5, 130.8, 129.7, 129.4, 129.4,
127.9, 127.7.
(E)-1-(Trifluoromethyl)-4-(2-(phenylsulfonyl)vinyl)benze-
ne (2f)[20]. White solid, yield 30%, 18.7 mg, mp 132-133 C. H
NMR (400 MHz, CDCl3) δ 7.97 (d, J = 7.4 Hz, 2H), 7.73 – 7.65 (m, 4H),
7.61 – 7.56 (m, 4H), 6.95 (d, J = 15.4 Hz, 1H). 13C NMR (100 MHz,
CDCl3) δ 140.4, 140.1, 135.7, 133.7, 132.6(q, J = 32.7 Hz), 130.0,
o
1
Experimental procedure for the synthesis of 2a: A 10 mL
oven-dried reaction vessel was charged with Paraformaldehyde(1.8
mmol, 54 mg) , Et3N (0.8 equiv., 23 μL), (benzylsulfonyl)benzene
(0.2 mmol, 46.4 mg), and DMF (0.4 mL) under Ar. The sealed
reaction vessel was stirred at 140 oC for 18 h. After cooling to room
temperature, the reaction was diluted with ethyl acetate and
129.5, 128.7, 127.8, 126.0(q, J = 3.6 Hz), 123.6 (q, J = 270.8 Hz). 19
NMR (376 MHz, CDCl3) δ -63.0.
F
4 | J. Name., 2012, 00, 1-3
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Page 5 of 10
Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
(E)-1-(2-(phenylsulfonyl)vinyl)-4-(trifluoromethoxy)benz- 7.38 (m, 3H), 7.25 – 7.20 (m, 2H), 6.85 (d, J = 15.4 Hz,V1ieHw)A.rt1i3cCle ONnMlinRe
[4]
o
1
ene(2g) . White solid, yield 37%, 24.3 mg, mp 90-92 C. H NMR (100 MHz, CDCl3) δ 165.6(d, J = 254.4 HzD) O, I:11402.1.603, 91/3D60.O7B, 0103326.21J,
(400 MHz, CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7. 69 – 7. 62 (m, 2H), 131.3, 130.5(d, J = 9.5 Hz), 129.1, 128.6, 127.0, 116.6(d, J = 22.5 Hz).
7.58 – 7.52 (m, 4H), 7.24 (d, J = 8.2 Hz, 2H), 6.85 (d, J = 15.4 Hz, 1H). 19F NMR (376 MHz, CDCl3) δ -103.9.
13C NMR (100 MHz, CDCl3) δ 151.0, 140.7, 140.4, 133.6, 130.9, 130.2,
(E)-1-chloro-4-(styrylsulfonyl)benzene (2p)[19]. White solid,
129.5, 128.3, 127.7, 121.3, 117.7 (q, J = 254.1 Hz). 19F NMR (376
MHz, CDCl3) δ -57.7. HRMS m/z calcd for: C15H12F3O3S+ (M+H)+
o
1
yield 69%, 38.5 mg, mp 82-83 C. H NMR (400 MHz, CDCl3) δ 7.89
(d, J = 8.6 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.54 – 7.49 (m, 4H), 7.44
– 7.38 (m, 3H), 6.84 (d, J = 15.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
143.1, 140.1, 139.2, 132.2, 131.4, 129.7, 129.2, 128.6, 126.8.
329.0454, found 329.0451.
(E)-1-Methyl-3-[2-(phenylsulfonyl)vinyl]benzene (2h)[20]
.
White solid, yield 56%, 29.0 mg, mp 105-106 oC. 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J = 7.4 Hz, 2H), 7.68 – 7.53 (m, 4H), 7.29 – 7.23 (m,
5H), 6.84 (d, J = 15.0 Hz, 1H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 142.7, 140.8, 138.8, 133.3, 132.3, 132.1, 129.3, 129.1, 129.0,
127.6, 127.0, 125.8, 21.3.
(E)-1-bromo-4-(styrylsulfonyl)benzene (2q)[19]. White solid,
o
1
yield 74%, 47.8 mg, mp 102-103 C. H NMR (400 MHz, CDCl3) δ
7.81 (d, J = 8.4 Hz, 2H), 7.71 – 7.66 (m, 3H), 7.50 – 7.39 (m, 5H), 6.83
(d, J = 15.4 Hz, 1H). 13C NMR (100MHz, CDCl3) δ 143.1, 139.8, 132.7,
132.2, 131.5, 129.4, 129.2, 129.1, 128.7, 126.9.
(E)-2-(2-(phenylsulfonyl)vinyl)benzonitrile(2i). White solid,
(E)-1-(styrylsulfonyl)-4-(trifluoromethyl)benzene (2r)[21]
.
o
1
yield 22%, 11.8 mg, mp 121-122 C. H NMR (400 MHz, CDCl3) δ
7.99 (d, J = 7.2 Hz, 2H), 7.93 (d, J = 15.4 Hz, 1H), 7.73 (d, J = 7.8 Hz,
1H), 7.68 – 7.57 (m, 5H), 7.54 – 7.50 (m, 1H), 7.14 (d, J = 15.4 Hz,
1H). 13C NMR (100 MHz, CDCl3) δ 139.8, 137.3, 135.2, 133.8, 133.9,
133.1, 132.5, 130.9, 129.5, 128.1, 128.0, 116.7, 112.9. HRMS calcd
for: C15H12NO2S+ (M+H)+ 270.0583, found 270.0587.
o
1
White solid, yield 85%, 53.1 mg, mp 77-79 C. H NMR (400 MHz,
CDCl3) δ 8.09 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.0 Hz, 2H), 7.75 (d, J =
15.4 Hz, 1H), 7.50 (d, J = 7.4 Hz, 2H), 7.41 – 7.39 (m, 3H), 6.86 (d, J =
15.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 144.3, 144.0, 135.0(q, J =
32.9 Hz), 131.9, 131.6, 129.1, 128.7, 128.2, 126.4(q, J = 3.7 Hz),
126.2, 123.1(q, J = 271.2 Hz). 19F NMR (376 MHz, CDCl3) δ -63.3.
(E)-1-fluoro-2-(2-(phenylsulfonyl)vinyl)benzene
(2j).
(E)-2-(2-(phenylsulfonyl)vinyl)naphthalene (2t). White
solid, yield 52%, 30.6 mg, mp 98-100 oC. 1H NMR (400 MHz, CDCl3) δ
7.99 (d, J = 7.2 Hz, 2H), 7.92 (s, 1H), 7.86 – 7.79 (m, 4H), 7.63 –7.49
(m, 6H), 6.97 (d, J = 15.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.5,
140.7, 134.4, 133.3, 133.0, 131.0, 130.9, 129.7, 129.3, 128.9, 128.6,
127.8, 127.6, 127.2, 126.9, 123.3. HRMS calcd for: C18H15O2S+
(M+H)+ 295.0787, found 295.0793.
White solid, yield 87%, 45.6 mg, mp 130-131 oC. 1H NMR (400 MHz,
CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.77 (d, J = 15.6 Hz, 1H), 7.66 – 7.54
(m, 3H), 7.49 – 7.38 (m, 2H), 7.20 – 7.09 (m, 2H), 7.03 (d, J = 15.6 Hz,
1H). 13C NMR (100 MHz, CDCl3) δ 161.5(d, J = 253.8 Hz), 140.4, 135.5,
133.5, 132.8(d, J = 8.9 Hz), 130.3(d, J = 2.6 Hz), 130.1(d, J = 8.6 Hz),
129.4, 127.7, 124.7(d, J = 3.6 Hz), 120.5(d, J = 11.7 Hz), 116.4(d, J =
21.6 Hz). 19F NMR (376 MHz, CDCl3) δ -112.3. HRMS calcd for:
C14H12FO2S+ (M+H)+ 263.0537, found 263.0532.
(E)-2-(2-((4-chlorophenyl)sulfonyl)vinyl)naphthalene (2u).
White solid, yield 48%, 31.6 mg, mp 182-183 oC. 1H NMR (400 MHz,
CDCl3) δ 7.95 – 7.84 (m, 7H), 7.57 – 7.52 (m, 5H), 6.94 (d, J = 15.4 Hz,
1H). 13C NMR (100 MHz, CDCl3) δ 143.1, 140.0, 139.3, 134.5, 133.0,
131.1, 129.6, 129.7, 129.1, 129.0, 128.7, 127.9, 127.8, 127.0, 126.8,
123.3. HRMS calcd for: C18H14ClO2S+ (M+H)+ 329.0397, found
329.0394.
(E)-1-methyl-4-(styrylsulfonyl)benzene (2l)[19]. White solid,
o
1
yield 38%, 19.6 mg, mp 119-120 C. H NMR (400 MHz, CDCl3) δ
7.83 (d, J = 8.2 Hz, 2H), 7.66 (d, J = 15.4 Hz, 1H), 7.49 –7.47 (m, 2H),
7.42 – 7.34 (m, 5H), 6.85 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 144.4, 142.0, 137.8, 132.5, 131.1, 130.0, 129.1,
128.5, 127.7, 127.6, 21.6.
(E)-2-(2-(phenylsulfonyl)vinyl)quinoline (2v). White solid,
(E)-1-ethyl-4-(styrylsulfonyl)benzene(2m). White solid, yield
49%, 26.7 mg, mp 71-72 oC. 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J =
8.2 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.49 – 7.48(m, 2H), 7.41 – 7.36
(m, 5H), 6.85 (d, J = 15.4 Hz, 1H), 2.73 (q, J = 7.6 Hz, 2H), 1.26 (t, J =
7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 150.5, 142.0, 137.9, 132.4,
131.1, 129.0, 128.8, 128.5, 127.8, 127.6, 28.9, 15.1. HRMS m/z calcd
for: C16H17O2S+ (M+H)+ 273.0944, found 273.0949.
o
1
yield 23%, 13.6 mg, mp 139-140 C. H NMR (400 MHz, CDCl3) δ
8.23 (d, J = 8.4 Hz, 1H), 8.10 (d, J = 8.2 Hz, 1H), 8.02 (d, J = 7.4 Hz,
2H), 7.85 (t, J = 11.8 Hz, 2H), 7.78 –7.74 (m, 1H), 7.67 – 7.55 (m, 6H).
13C NMR (100 MHz, CDCl3) δ 150.9, 147.9, 140.9, 140.1, 137.4, 133.7,
133.3, 130.6, 129.6, 129.4, 128.4, 128.0, 128.0, 127.6, 121.5. HRMS
calcd for: C17H14NO2S+ (M+H)+ 296.0739, found 296.0735.
(1-(phenylsulfonyl)vinyl)benzene (3a)[22]. White solid, yield
86%, 41.9 mg, mp 70-71 oC. 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J =
7.2 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.44 – 7.40 (m, 2H), 7.35 – 7.28
(m, 5H), 6.65 (s, 1H), 5.98 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 150.8,
138.5, 133.4, 132.3, 129.3, 129.1, 128.8, 128.3, 128.2, 126.0.
(E)-1-(tert-butyl)-4-(styrylsulfonyl)benzene (2n). White
solid, yield 78%, 46.9 mg, mp 111-112 oC. 1H NMR (400 MHz, CDCl3)
δ 7.86 (d, J = 7.0 Hz, 2H), 7.67 (d, J = 15.2 Hz, 1H), 7.55 (d, J = 7.2 Hz,
2H), 7.48 (d, J = 6.8 Hz, 2H), 7.40 – 7.37 (s, 3H), 6.86 (d, J = 15.2 Hz,
1H), 1.34 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 157.3, 141.9, 137.6,
132.4, 131.1, 129.0, 128.5, 127.6, 127.5, 126.4, 35.2, 31.0. HRMS 1-methyl-4-(1-(phenylsulfonyl)vinyl)benzene
(3b)[22]
.
o
1
calcd for: C18H21O2S+ (M+H)+ 301.1257, found 301.1259.
White solid, yield 75%, 38.7 mg, mp 85-86 C. H NMR (400 MHz,
CDCl3) δ 7.70 (d, J = 7.2 Hz, 2H), 7.53 (t, J = 7.4 Hz, 1H), 7.41 (t, J =
7.8 Hz, 2H), 7.22 (d, J = 8.2 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 6.60 (s,
1H), 5.93 (s, 1H), 2.32 (s, 3H).13C NMR (100 MHz, CDCl3) δ 150.7,
139.4, 138.8, 133.3, 129.4, 129.0, 128.9, 128.8, 128.3, 125.5, 21.2.
(E)-1-fluoro-4-(styrylsulfonyl)benzene (2o)[19]. White solid,
yield 74%, 38.8 mg, mp 85-86 oC. 1H NMR (400 MHz, CDCl3) δ 7.99 –
7.94 (m, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.50 – 7.48 (m, 2H), 7.43 –
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Organic & Biomolecular Chemistry
Page 6 of 10
ARTICLE
Journal Name
1-chloro-4-(1-(phenylsulfonyl)vinyl)benzene (3c)[15]. White 129.2, 129.1, 128.7, 128.6, 128.2. HRMS (ESI) m/z calcd for:
View Article Online
+
+
solid, yield 80%, 44.5 mg, mp 71-73 oC. 1H NMR (400 MHz, CDCl3) δ C14H11Cl2O2S (M+H) 312.9851, found 312.9855.
DOI: 10.1039/D0OB00362J
7.69 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H),
1-ethyl-4-((1-phenylvinyl)sulfonyl)benzene (3k)[19]
7.29 – 7.24 (m, 4H), 6.64 (s, 1H), 5.96 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ 149.7, 138.3, 135.6, 133.6, 130.8, 130.4, 129.0, 128.5,
.
Pale
yellow viscous liquid, yield 83%, 45.1 mg. 1H NMR (400 MHz, CDCl3)
δ 7.58 (d, J = 8.4 Hz, 2H), 7.33 – 7.31 (m, 3H), 7.28 – 7.24 (m, 2H),
7.21 (d, J = 8.2 Hz, 2H), 6.59 (s, 1H), 5.93 (s, 1H), 2.65 (q, J = 7.6 Hz,
2H), 1.20 (t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 151.0,
128.2, 126.4.
1-bromo-4-(1-(phenylsulfonyl)vinyl)benzene
White solid, yield 70%, 45.2 mg, mp 76-77 C. H NMR (400 MHz, 150.4, 135.8, 132.5, 129.2, 129.0, 128.4, 128.3, 128.2, 125.5 , 28.7,
CDCl3) δ 7.69 (d, J = 7.2 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H), 7.45 – 7.40 14.9.
(m, 4H), 7.20 (d, J = 8.4 Hz, 2H), 6.64 (s, 1H), 5.96 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ 150.0, 138.4, 133.6, 131.5, 131.4, 130.6, 129.0,
128.3, 126.3, 123.9.
(3d)[15]
.
o
1
1-(tert-butyl)-4-((1-phenylvinyl)sulfonyl)benzene
(3l).
o
1
White solid, yield 86%, 51.6 mg, mp 85-86 C. H NMR (400 MHz,
CDCl3) δ 7.60 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.35 – 7.31
1-nitro-4-(1-(phenylsulfonyl)vinyl)benzene (3e). White (m, 3H), 7.28 – 7.24 (m, 2H), 6.58 (s, 1H), 5.93 (s, 1H), 1.28 (s, 9H).
solid, yield 45%, 26.0 mg, mp 113-115 oC. 1H NMR (400 MHz, CDCl3) 13C NMR (100 MHz, CDCl3) δ 157.2, 150.9, 135.6, 132.5, 129.2, 129.1,
δ 8.15 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.2 Hz, 2H), 7.60 – 7.53 (m, 3H), 128.2, 128.1, 125.8, 125.6, 35.1, 30.9. HRMS (ESI) m/z calcd for:
7.45 (t, J = 7.6 Hz, 2H), 6.77 (s, 1H), 6.08 (s, 1H). 13C NMR (100 MHz, C18H21O2S+ (M+H)+301.1257, found 301.1255.
CDCl3) δ 149.4, 148.3, 138.9, 138.0, 133.9, 130.1, 129.2, 128.3,
1-fluoro-4-((1-phenylvinyl)sulfonyl)benzene
(3m)[14]
.
127.7, 123.5. HRMS (ESI) m/z calcd for: C14H12NO4S+ (M+H)+
290.0481, found 290.0488.
o
1
White solid, yield 83%, 43.4 mg, mp 92-93 C. H NMR (400 MHz,
CDCl3) δ 7.70 – 7.66 (m, 2H), 7.36 – 7.26 (m, 5H), 7.06 (t, J = 8.6 Hz,
2H), 6.63 (s, 1H), 5.96 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 165.5 (d,
1-methyl-3-(1-(phenylsulfonyl)vinyl)benzene
(3f)[15]
.
o
1
White solid, yield 82%, 42.3 mg, mp 82-83 C. H NMR (400 MHz, J = 254.5 Hz), 150.7, 134.5 (d, J = 3.3 Hz), 132.1, 131.2 (d, J = 9.5 Hz),
CDCl3) δ 7.70 (d, J = 7.3 Hz, 1H), 7.53 (t, J = 7.0 Hz, 1H), 7.46 (t, J = 129.4, 129.0, 128.3, 126.0, 116.1 (d, J = 22.8 Hz). 19F NMR (376 MHz,
7.6 Hz, 2H), 7.16 – 7.09 (m, 4H), 6.60 (s, 1H), 5.94 (s, 1H), 2.28 (s, CDCl3) δ -102.3.
3H). 13C NMR (100 MHz, CDCl3) δ 150.8, 138.6, 137.9, 133.3, 132.2,
130.0, 129.6, 128.8, 128.3, 128.1, 126.1, 125.7, 21.2.
1-chloro-4-((1-phenylvinyl)sulfonyl)benzene
(3n)[15]
.
o
1
White solid, yield 69%, 38.3 mg, mp 87-88 C. H NMR (400 MHz,
1-methyl-2-(1-(phenylsulfonyl)vinyl)benzene
(3g)[22]
.
CDCl3) δ 7.60 (d, J = 8.6 Hz, 2H), 7.37 – 7.28 (m, 7H), 6.65 (s, 1H),
White solid, yield 87%, 44.9 mg, mp 80-81oC. H NMR (400 MHz, 5.98 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 150.4, 140.0, 137.1, 132.0,
CDCl3) δ 7.65 – 7.58 (m, 3H), 7.44 (t, J = 7.8 Hz, 2H), 7.29 – 7.23 (m, 129.7, 129.5, 129.1, 129.0, 128.3, 126.3.
1H), 7.13 – 7.07 (m, 2H), 6.96 (d, J = 7.8 Hz, 1H), 6.77 (s, 1H), 5.84 (s,
1
1-bromo-4-((1-phenylvinyl)sulfonyl)benzene
(3o)[15]
.
1H), 1.95 (s, 3H).13C NMR (100 MHz, CDCl3) δ 149.9, 138.2, 137.7,
133.5, 131.4, 130.6, 130.1, 129.2, 128.9, 128.8, 126.9, 125.1, 19.2.
o
1
White solid, yield 74%, 47.8 mg, mp 80-81 C. H NMR (400 MHz,
CDCl3) δ 7.53 (s, 4H), 7.38 – 7.27 (m, 5H), 6.65 (s, 1H), 5.99 (s, 1H).
1-fluoro-2-(1-(phenylsulfonyl)vinyl)benzene (3h). White 13C NMR (100 MHz, CDCl3) δ 150.4, 137.7, 132.1, 132.0, 129.8, 129.5,
solid, yield 85%, 44.5 mg, mp 87-89 oC. 1H NMR (400 MHz, CDCl3) δ 129.4, 128.7, 128.4, 126.4.
7.67 (d, J = 7.6 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.41 (t, J = 7.6 Hz, 3H),
1-((1-phenylvinyl)sulfonyl)-4-(trifluoromethyl)benzene
7.33 – 7.28 (m, 1H), 7.10 (t, J = 7.4 Hz, 1H), 6.92 (t, J = 9.0 Hz, 1H),
(3p)[23]. White solid, yield 72%, 44.9 mg, mp 80-82 C. H NMR
(400 MHz, CDCl3) δ 7.80 (d, J = 12.2 Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H),
7.38 – 7.27 (m, 5H), 6.70 (s, 1H), 6.05 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ 150.1, 142.3, 134.9 (q, J = 32.8 Hz), 131.8, 129.6, 129.1,
o
1
6.85 (s, 1H), 6.03 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 159.8 (d, J =
248.9 Hz), 144.1, 138.2, 133.6, 131.7 (d, J = 1.7 Hz), 131.3(d, J = 8.0
Hz), 128.9, 128.8, 128.4, 123.7 (d, J = 3.8 Hz), 119.8 (d, J = 15.0 Hz),
115.5(d, J = 21.9 Hz). 19F NMR (376 MHz, CDCl3) δ -115.0. HRMS (ESI)
m/z calcd for: C14H12FO2S+ (M+H)+ 263.0537, found 263.0539.
128.8, 128.5, 127.2, 125.9 (q, J = 3.8 Hz), 123.0 (q, J = 271.5 Hz). 19
NMR (376 MHz, CDCl3) δ -63.2.
F
2-(1-(phenylsulfonyl)vinyl)benzonitrile (3i). White solid,
yield 49%, 26.9 mg, mp 99-100 oC. 1H NMR (400 MHz, CDCl3) δ 7.77
(d, J = 7.4 Hz, 1H), 7.67 (d, J = 7.4 Hz, 2H) , 7.60(m, 2H), 7.54 (d, J =
7.4 Hz, 1H), 7.48 – 7.43 (m, 3H), 6.93 (s, 1H), 6.13 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ 147.1, 137.5, 135.5, 134.0, 132.9, 132.3, 131.1,
129.7, 129.5, 129.2, 128.7, 116.4, 113.4. HRMS (ESI) m/z calcd for:
C15H12NO2S+ (M+H)+270.0583, found 270.0588.
2-(1-(phenylsulfonyl)vinyl)naphthalene (3q)[15]. White solid,
o
1
yield 62%, 36.5 mg, mp 71-72 C. H NMR (400 MHz, CDCl3) δ 7.87
(s, 1H), 7.82 – 7.72 (m, 5H), 7.53 – 7.43 (m, 4H), 7.37 (t, J = 7.8 Hz,
2H), 6.74 (s, 1H), 6.08 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 150.8,
138.6, 133.4, 133.2, 132.6, 129.7, 128.9, 128.8, 128.3, 128.2, 128.0,
127.5, 127.0, 126.5, 126.6, 126.1.
1-((1-phenylvinyl)sulfonyl)naphthalene (3r)[15]. White solid,
1,3-dichloro-2-(1-(phenylsulfonyl)vinyl)benzene
(3j).
o
1
yield 52%, 30.6mg, mp 99-100 C. H NMR (400 MHz, CDCl3) δ 8.59
(d, J = 8.6 Hz, 1H), 8.12 (d, J = 7.4 Hz, 1H), 8.00 (d, J = 8.2 Hz, 1H),
7.89 (d, J = 8.0 Hz, 1H), 7.65 – 7.55 (m, 2H), 7.41 (t, J = 7.8 Hz, 1H),
7.23 – 7.10 (m, 5H), 6.77 (s, 1H), 6.04 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ 151.2, 135.0, 133.6, 132.6, 132.0, 131.2, 129.0, 128.9,
128.5, 128.4, 128.1, 127.9, 126.6, 125.6, 123.9, 123.9.
White solid, yield 87%, 54.5 mg, mp 113-114 oC. 1H NMR (400 MHz,
CDCl3) δ 7.70 (d, J = 7.8 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.42 (t, J =
7.6 Hz, 2H), 7.26 – 7.17 (m, 3H), 6.85 (s, 1H), 5.98 (s, 1H). 13C NMR
(100 MHz, CDCl3) δ 147.2, 139.1, 136.4, 133.9, 131.4, 131.0, 130.8,
6 | J. Name., 2012, 00, 1-3
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Page 7 of 10
Organic & Biomolecular Chemistry
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(1-(methylsulfonyl)vinyl)benzene (3s)[14]. Pale yellow viscous 1H), 3.20 – 3.14 (m, 1H), 2.68 – 2.60 (m, 4H), 2.43 – 2.39 (m, 4H). 13C
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1
DOI: 10.1039/D0OB00362J
liquid, yield 74%, 26.9 mg. H NMR (400 MHz, CDCl3) δ 7.64 –7.62 NMR (100 MHz, CDCl3) δ 138.1, 133.4, 132.5, 129.8, 128.7, 128.6,
(m, 2H), 7.48 – 7.41 (m, 3H), 6.54 (s, 1H), 6.03 (s, 1H), 2.80 (s, 3H). 128.4, 68.8, 57.3, 54.6, 27.6. HRMS calcd for: C18H22NO2S2 (M+H)+
13C NMR (100 MHz, CDCl3) δ 149.9, 132.4, 129.8, 128.8, 128.5, 125.9, 348.1086, found 348.1086.
+
40.5.
1-methyl-4-(2-phenyl-2-(phenylsulfonyl)ethyl)piperazine
(1-(ethylsulfonyl)vinyl)benzene (3t)[14]. Pale yellow viscous (5d). White solid, yield 92%, 63.3 mg, mp 113-114 oC. 1H NMR (400
liquid, yield 72%, 28.2 mg. 1H NMR (400 MHz, CDCl3) δ 7.62 (m, 2H), MHz, CDCl3) δ 7.55 (m, 3H), 7.39 (t, J = 7.8 Hz, 2H), 7.31 – 7.22 (m,
7.46 – 7.39 (m, 3H), 6.52 (s, 1H), 6.08 (s, 1H), 2.85 (q, J = 7.4 Hz, 1H)., 3H), 7.16 (d, J = 7.2 Hz, 2H), 4.34– 4.31 (m, 1H), 3.56 – 3.51 (m, 1H),
1.22 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 147.8, 132.5, 3.17 – 3.12 (m, 1H), 2.39 (s, 4H), 2.22 – 2.05 (m, 7H). 13C NMR (100
129.7, 128.8, 128.5, 127.5, 46.2, 6.9.
MHz, CDCl3) δ 137.9, 133.3, 132.4, 129.8, 128.7, 128.6, 128.5, 128.3,
68.8, 56.2, 54.5, 52.6, 45.7. HRMS calcd for: C19H25N2O2S+ (M+H)+
345.1631, found 345.1634.
(1-(cyclopropylsulfonyl)vinyl)benzene (3u)[14]. Pale yellow
viscous liquid, yield 79%, 32.8 mg. 1H NMR (400 MHz, CDCl3) δ 7.51
(m, 2H), 6.42 (s, 1H), 5.94 (s, 1H), 2.25 – 2.20 (m, 1H), 1.12 – 1.11 (m, 1-(2-phenyl-2-(phenylsulfonyl)ethyl)piperidin-4-one (5e).
2H), 0.89 – 0.88 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 149.6, 132.9, White solid, yield 60%, 41.1 mg, mp 152-153 oC. 1H NMR (400 MHz,
129.5, 128.9, 128.5, 125.2, 29.4, 5.4.
CDCl3) δ 7.63 – 7.51 (m, 3H), 7.40 (t, J = 7.8 Hz, 2H), 7.35 – 7.22 (m,
4H), 7.18 (d, J = 6.8 Hz, 2H), 4.38 – 4.27 (m, 1H), 3.71 – 3.61 (m, 1H),
3.30 –3.25(m, 1H), 2.79 – 2.50 (m, 4H), 2.35 – 2.14 (m, 4H). 13C NMR
(100 MHz, CDCl3) δ 208.3, 138.0, 133.5, 132.1, 129.7, 128.8, 128.7,
128.6, 128.5, 128.5, 69.4, 55.4, 52.8, 40.8. HRMS calcd for:
C19H22NO3S+ (M+H)+ 344.1315, found 344.1305.
2-((1-phenylvinyl)sulfonyl)naphthalene (3v)[15]. White solid,
yield 61%, 35.8 mg, mp 90-91 oC. 1H NMR (400 MHz, CDCl3) δ 8.29 (s,
1H), 7.88 – 7.84 (m, 3H), 7.65 – 7.55 (m, 3H), 7.35 – 7.22 (m, 5H),
6.70 (s, 1H), 6.01 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 150.8, 135.5,
135.0, 132.4, 131.9, 130.1, 129.3, 129.3, 129.1, 129.1, 129.0, 128.2,
127.8, 127.4, 126.1, 122.9.
N-methyl-N-(2-phenyl-2-(phenylsulfonyl)ethyl)prop-2-
o
en-1-amine (5f). White solid, yield 77%, 48.5 mg, mp 80-81 C.
2-(1-(phenylsulfonyl)vinyl)quinoline (3w). Yellow solid, yield
50%, 29.5 mg, mp 89-90 oC. 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J =
8.4 Hz, 1H), 7.97 – 7.89 (m, 4H), 7.80 (d, J = 7.4 Hz, 1H), 7.71 – 7.67
(m, 1H), 7.57 – 7.44 (m, 4H), 6.95 (s, 1H), 6.73 (s, 1H). 13C NMR (100
MHz, CDCl3) δ 150.6, 150.2, 147.6, 139.7, 136.7, 133.4, 130.0, 129.5,
129.4, 128.8, 128.5, 127.5, 127.4, 127.3, 120.1. HRMS calcd for:
C17H14NO2S+ (M+H)+ 296.0739, found 296.0735.
1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 9.6 Hz, 3H), 7.38 (t, J = 7.6
Hz, 2H), 7.29 – 7.22 (m, 3H), 7.14 (d, J = 7.0 Hz, 2H), 5.69 – 5.59 (m,
1H), 5.09 – 5.05 (m, 2H), 4.31 –4.28 (m , 1H), 3.41 – 3.23 (m, 2H),
3.02 – 2.91 (m, 2H), 2.13 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 137.6,
134.8, 133.4, 132.2, 129.9, 128.8, 128.6, 128.5, 128.3, 118.0, 69.7,
60.8, 54.3, 42.3. HRMS calcd for: C18H22NO2S+ (M+H)+ 316.1366,
found 316.1364.
(sulfonylbis(ethene-1,1-diyl))dibenzene (3x). Pale yellow
viscous liquid, yield 30%, 16.2 mg. 1H NMR (400 MHz, CDCl3) δ 7.39
– 7.27 (m, 10H), 6.41 (s, 2H), 5.92 (s, 2H). 13C NMR (100 MHz, CDCl3)
δ 148.3, 132.2, 129.4, 128.9, 128.3, 128.0. HRMS calcd for:
C16H15O2S+ (M+H)+ 270.0715, found 270.0715.
2-(2-phenyl-2-(phenylsulfonyl)ethyl)-1,2,3,4-tetrahydro-
isoquinoline (5g). White solid, yield 86%, 65.0 mg, mp 124-125
1
oC. H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 4.2 Hz, 1H), 7.50 (t, J =
7.4 Hz, 1H), 7.37 – 7.20(m, 7H), 7.11 – 7.00 (m, 3H), 6.90 (d, J = 8.4
Hz, 1H), 4.44 – 4.40 (m, 1H), 3.69 – 3.52 (m, 3H), 3.37 – 3.31 (m, 1H),
1-(2-phenyl-2-(phenylsulfonyl)ethyl)piperidine (5a). White 2.74 – 2.63 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 137.8, 134.1, 133.9,
solid, yield 73%, 48.1 mg, mp 100-101 oC. 1H NMR (400 MHz, CDCl3) 133.3, 132.5, 129.9, 128.8, 128.7, 128.5, 128.4, 126.4, 126.1, 125.5,
δ 7.59 – 7.52 (m, 3H), 7.39 (t, J = 7.8 Hz, 2H), 7.31 – 7.23 (m, 3H), 69.6, 55.9, 55.6, 50.6, 28.7. HRMS calcd for C23H24NO2S+ (M+H)+
7.18 (d, J = 6.6 Hz, 2H), 4.35 – 4.31 (m, 1H), 3.50 – 3.46 (m, 1H), 3.10 378.1522, found 378.1528.
– 3.05 (m, 1H), 2.28 – 2.22 (m, 4H), 1.33 – 1.28 (m, 6H). 13C NMR
(2-phenyl-2-(phenylsulfonyl)ethyl)(p-tolyl)sulfane (5h).
(100 MHz, CDCl3) δ 138.2, 133.2, 132.7, 129.9, 128.7, 128.5, 128.5,
White solid, yield 86%, 63.3 mg, mp 133-134 oC. 1H NMR (400 MHz,
128.3, 69.0, 57.2, 54.3, 25.6, 23.8. HRMS calcd for: C19H24NO2S+
CDCl3) δ 7.55 (t, J = 7.4 Hz, 1H), 7.48 (d, J = 8.0 Hz, 2H), 7.37 (t, J =
(M+H)+ 330.1522, found 330.1522.
7.6 Hz, 2H), 7.31 (t, J = 7.2 Hz, 1H), 7.24 (t, J = 8.6 Hz, 3H), 7.12 (d, J
4-(2-phenyl-2-(phenylsulfonyl)ethyl)morpholine
(5b). = 8.0 Hz, 2H), 7.07 – 7.05 (m, 4H), 4.16 – 4.12 (m, 1H), 3.95 – 3.91
White solid, yield 72%, 47.7 mg, mp 108-110 oC. 1H NMR (400 MHz, (m, 1H), 3.47 (t, J = 12.8 Hz, 1H), 2.33 (s, 3H).13C NMR (100 MHz,
CDCl3) δ 7.59 – 7.53 (m, 3H), 7.39 (t, J = 7.8 Hz, 2H), 7.31 – 7.22 (m, CDCl3) δ 137.3, 136.9, 133.7, 131.1, 130.8, 130.1, 130.0, 129.9,
3H), 7.16 (d, J = 6.8 Hz, 2H), 4.34 – 4.32 (m, 1H), 3.51 – 3.45 (m, 5H), 129.1, 129.0, 128.7, 128.4, 70.3, 32.6, 21.1. HRMS calcd for:
3.13 –3.09 (m, 1H), 2.37 – 2.33 (m, 4H). 13C NMR (100 MHz, CDCl3) δ C21H21O2S2+ (M+H)+ 369.0977, found 369.0973.
138.0, 133.4, 132.3, 129.8, 128.8, 128.7, 128.5, 128.4, 68.9, 66.5,
1-((2-methoxy-1-phenylethyl)sulfonyl)-4-methylbenzen
56.8, 53.3. HRMS calcd for: C18H22NO3S+ (M+H)+ 332.1315, found
o
1
(5i). White solid, yield 39.8%, 72.0 mg, mp 119-120 C. H NMR
(400 MHz, CDCl3) δ 7.45 (d, J = 8.2 Hz, 2H), 7.33 – 7.25 (m, 3H), 7.19
332.1317.
4-(2-phenyl-2-(phenylsulfonyl)ethyl)thiomorpholine (5c). (d, J = 7.8 Hz, 4H), 4.40 – 4.37 (m, 1H), 4.28 – 4.26 (m, 1H), 4.07 –
White solid, yield 75%, 52.1 mg, mp 129-130 oC. 1H NMR (400 MHz, 4.03 (m, 1H), 3.30 (s, 3H), 2.39 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
CDCl3) δ 7.59 –7.53 (m, 3H), 7.39 (t, J = 7.6 Hz, 2H), 7.29 – 7.23 (m, 144.6, 134.8, 131.2, 129.8, 129.2, 128.9, 128.9, 128.5, 70.7, 69.8,
3H), 7.16 (d, J = 7.2 Hz, 2H), 4.32– 4. 29 (m, 1H), 3.57 – 3. 52 (m,
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Organic & Biomolecular Chemistry
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59.1, 21.6. HRMS calcd for: C16H19O3S+ (M+H)+ 291.1049, found
291.1051.
Commun., 2016, 52, 10415; (d) K. H. Oh, S. M. Kim, S. Y. Park
View Article Online
and J. K. Park, Org. Lett., 2016, 18, 22D0O4;I:(1e0).1I0.3J9./BDa0rOvBe0,0W36.-2JJ.
Chang, Y.-T. Lin, T. U. Thikekar and C.-M. Sun, ACS Comb. Sci.,
2019, 21, 269; (f) X. Zhang, T.-L. Wang, C.-D. Huo, X.-C. Wang
and Z.-J. Quan, Chem. Commun., 2018, 54, 3114; (g) J. Sheng,
K.-J. Bian, Y.-M. Su, G.-X. Liao, R.-M. Duan, C. Li, Z.-H. Liu and
X.-S. Wang, Org. Chem. Front., 2020, 7, 617.
methyl(2-phenyl-2-tosylethyl)sulfane (5j). White solid, yield
71%, 43.4 mg, mp 110-111 oC. 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J
= 7.6 Hz, 2H)), 7.33 – 7.24 (m, 4H), 7.19 – 7.13 (m, 3H), 4.23 (d, J =
14.2 Hz, 1H), 3.52 – 3.48 (m, 1H), 3.24 (t, J = 12.6, 1H), 2.39 (s, 3H),
1.97 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 144.8, 134.0, 131.5, 130.8,
129.9, 129.4, 129.0, 128.4, 32.1, 21.6, 16.2. HRMS calcd for:
C16H19O2S2+ (M+H)+ 306.0748, found 306.0750.
6
7
(a) D. C. Meadows, T. Sanchez, N. Neamati, T. W. North and
J. Gervay-Hague, Bioorg. Med. Chem., 2007, 15, 1127; (b) G.
Pradel, R. Vicik, T. Schirmeister, N. Micale, S. Grasso and M.
Zappala, J. Med. Chem., 2008, 51, 988; (c) M. -D. Mertens, J.
Schmitz, M. Horn, N. Furtmann, J. Bajorath, M. Mareš and M.
Gütschow, ChemBioChem, 2014, 15, 955; (d) A. -S. Newton,
P. M. C. Glória, L. -M. Gonçalves, D. J. V. A. Santos, R.
Moreira, R. -C. Guedes and M. -M. -M. Santos, Eur. J. Med.
Chem., 2010, 45, 3858.
(a) N. -S. Simpkins, Sulfones in Organic Synthesis, Pergamon
Press: Oxford, 1993; (b) Q.-Q. Zhou, S. J. S. Düsel, L.-Q. Lu, B.
König and W.-J. Xiao, Chem. Commun., 2019, 55, 107; (c) L.
Shi, B. Wei, X. Yin, P. Xue, H. Lv and X. Zhang, Org. Lett.,
2017, 19, 1024; (d) Q. Shi, M. -C. Meehan, M. Galella, H.
Park, P. Khandelwal, J. Hynes, Jr., T. G. M. Dhar and D.
Marcoux, Org. Lett., 2018, 20, 337; (e) K. Yoshida and T.
Hayashi, J. Am. Chem. Soc., 2003, 125, 2872; (f) M. Ociepa, J.
Turkowska and D. Gryko, ACS Catal., 2018, 8, 11362; (g) J.
Wu, P. S. Grant, X. Li, A. Noble and V. K. Aggarwal, Angew.
Chem., Int. Ed., 2019, 58, 5697.
(a) Y. Fang, Z. Luo and X. Xu, RSC Adv., 2016, 6, 59661; (b) G.
Qiu, K. Zhou, L. Gao and J. Wu, Org. Chem. Front., 2018, 5,
691; (c) A. J. Borah and G. Yan, Org. Biomol. Chem., 2015, 13,
8094; (d) W. Guo, K. Tao, W. Tan, M. Zhao, L. Zheng and X.
Fan, Org. Chem. Front., 2019, 6, 2048.
(a) G. Rong, J. Mao, H. Yan, Y. Zheng and G. Zhang, Org. Lett.,
2015, 17, 18; (b) Y. Xu, X. Tang, W. Hu, W. Wu and H. Jiang,
Green Chem., 2014, 16, 3720; (c) A. U. Meyer, S. Jäger, D. -P.ꢀ
Hari and B. König, Adv. Synth. Catal., 2015, 357, 5050; (d) Y.
Xu, J. Zhao, X. Tang, W. Wu and H. Jiang, Adv. Synth. Catal.,
2014, 356, 2029.
Acknowledgements
Supported by the National Natural Science Foundation of
China (21502160, 21871226 and 21572194), Scientific
Research Fund of Hunan Provincial Education Department
(19B564), the Collaborative Innovation Center of New
Chemical Technologies for Environmental Benignity and
Efficient Resource Utilization.
Conflicts of interest
There are no conflicts to declare.
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Notes and references
1
(a) D. C Blakemore, P. M Doyle and Y. M Fobian, Synthetic
Methods in Drug Discovery : Vol. 1; The Royal Society of
Chemistry, Cambridge, 2016; (b) L. Li, Z. Chen, X. Zhang and
Y. Jia, Chem. Rev., 2018, 118, 3752; (c) Y. Wei and M. Shi, ACS
Catal., 2016, 6, 2515; (d) Z. Qu, F. Zhang, G.-J. Deng and H.
Huang, Org. Lett., 2019, 21, 8239; (e) G. Zhan, W. Du and Y.-
C. Chen, Chem. Soc. Rev., 2017, 46, 1675.
10 (a) G. Rong, J. Mao, H. Yan, Y. Zheng and G. Zhang, J. Org.
Chem., 2015, 80, 4697; (b) Y. Zhao, Y.-L. Lai, K.-S. Du, D.-Z. Lin
and J.-M. Huang, J. Org. Chem., 2017, 82, 9655; (c) P. Qian, M.
Bi, J. Su, Z. Zha and Z. Wang, J. Org. Chem., 2017, 81, 4876; (d)
J.-P. Wan, D. Hu, F. Bai, L. Wei and Y. Liu, RSC Adv., 2016, 6,
73132; (e) X. Li, X. Shi, M. Fang and X. Xu, J. Org. Chem., 2013,
78, 9499; (f) X. Li, Y. Xu, W. Wu, C. Jiang, C. Qi and H. Jiang,
Chem. Eur. J., 2014, 20, 7911; (g) S. Tang, Y. Wu, W. Liao, R.
Bai, C. Liu and A. Lei, Chem. Commun., 2014, 50, 4496; (h) S.
Li, X. Li, F. Yang and Y. Wu, Org. Chem. Front., 2015, 2, 1076.
11 (a) W. Wei, J. Li, D. Yang, J. Wen, Y. Jiao, J. You and H. Wang,
Org. Biomol. Chem., 2014, 12, 1861; (b) W. Wei, J. Wen, D.
Yang, H. Jing, J.You and H. Wang, RSC Adv., 2015, 5, 4416.
12 (a) X. Liang, M. Xiong, H. Zhu, K. Shen and Y. Pan, J. Org.
Chem., 2019, 84, 11210; (b) L. Wang, H. Yue, D. Yang, H. Cui,
M. Zhu, J. Wang, W. Wei and H. Wang, J. Org. Chem., 2017,
82, 6857; (c) R. Mao, Z. Yuan, R. Zhang, Y. Ding, X. Fan and J.
Wu, Org. Chem. Front., 2016, 3, 1498.
13 (a) R.-J. Song, Y. Liu, Y.-Y. Liu and J.-H. Li, J. Org. Chem., 2011,
76, 1001; (b) S. Waiba, M. K. Barman and B. Maji, J. Org.
Chem., 2019, 84, 973; (c) R. Zhang, P. Xu, S.-Y. Wang and S.-J.
Ji, J. Org. Chem., 2019, 84, 12324; (d) T. Liu, Y. Ding, X. Fan
and J. Wu, Org. Chem. Front., 2018, 5, 3153.
14 Y. Xi, B. Dong, E. -J. McClain, Q. Wang, T. -L. Gregg, N. G.
Akhmedov, J. L. Petersen and X. Shi, Angew. Chem. Int. Ed.,
2014, 53, 4657.
2
3
(a) L. Ping, D. S. Chung, J. Bouffard and S. Lee, Chem. Soc.
Rev., 2017, 46, 4299; (b) Z. Chen, B. Wang, J. Zhang, W. Yu, Z.
Liu and Y. Zhang, Org. Chem. Front., 2015, 2, 1107; (c) K.
Yokoo and K. Mori, Chem. Commun., 2018, 54, 6927; (d) W.
Wei, H. Cui, D. Yang, H. Yue, C. He, Y. Zhang and H. Wang,
Green Chem., 2017, 19, 5608.
(a) Y.-C. Lee, K. Kumar and H. Waldmann, Angew. Chem., Int.
Ed., 2008, 47, 7075; (b) Z. Qiao and X. Jiang, Org. Lett., 2016,
18, 1550; (c) Y.-C. Lee, L. Knauer, K. Louven, C. Golz, C.
Strohmann, H. Waldmann and K. Kumar, Eur. J. Org. Chem.,
2018, 5688; (d) J.-J. Feng, T.-Y. Lin, C.-Z. Zhu, H. Wang, H.-H.
Wu and J. Zhang, J. Am. Chem. Soc., 2016, 138, 2178; (e) X.
Fang, Q. Li, R. Shi, H. Yao and A. Lin, Org. Lett., 2018, 20,
6084; (f) X. Zhang, Y. Gao, R. -D. Laishram, K. Li, Y. Yang, Y.
Zhan, Y. Luo and B. Fan, Org. Biomol. Chem., 2019, 17, 2174;
(g) B.-B. Zhan, J. Fan, L. Jin and B.-F. Shi, ACS Catal., 2019, 9,
3298.
(a) F.-P. Wu, J.-B. Peng, X. Qi, J. Ying and X.-F. Wu, Adv.
Synth. Catal., 2018, 360, 3412; (b) P. Ni, B. Li, H. Huang, F.
Xiao and G.-J. Deng, Green Chem., 2017, 19, 5553; (c) P.
Nareddy, F. Jordan and M. Szostak, Org. Biomol. Chem.,
2017, 15, 4783; (d) Y. Zhang, X.-K. Liu, Z.-G. Wu, Y. Wang and
Y. Pan, Org. Biomol. Chem., 2017, 15, 6901; (e) X. Zhang, T.-L.
Wang, X.-J. Liu, X.-C. Wang and Z.-J. Quan, Org. Biomol.
Chem., 2019, 17, 2379; (f) X. Ji, H. Huang, W. Xiong, K. Huang,
W. Wu and H. Jiang, J. Org. Chem., 2014, 79, 7005; (g) J.-B.
Peng and X.-F. Wu, Angew. Chem., Int. Ed., 2018, 57, 1152.
(a) J. Zhao, M. Jiang and J.-T. Liu, Org. Chem. Front., 2018, 5,
1155; (b) G. Gao, J. Yan, K. Yang, F. Chen and Q. Song, Green
Chem., 2017, 19, 3997; (c) Y. An, H. Xia and J. Wu, Chem.
4
15 H. Wang, Q. Lu, C.-W. Chiang, Y. Luo, J. Zhou, G. Wang and A.
Lei, Angew. Chem. Int. Ed., 2017, 56, 595.
16 (a) F. Xiao, S. Yuan, H. huang and G. -J. Deng, Synlett 2018, 29,
2693; (b) Z. Ke, Y. Zhang, X. Cui and F. Shi, Green Chem., 2016,
5
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ARTICLE
18, 808; (c) X. Xu, Y. Yang, X. Chen, X. Zhang and W. Yi, Org.
Biomol. Chem., 2017, 15, 9061; (d) J. Zhang, Q. Qian, M. Cui, C.
Chen, S. Liu and B. Han, Green Chem., 2017, 19, 4396; (e) X. Yi, H.
Tang, J. Chen, X. Xu and Y. Ma, Org. Chem. Front., 2018, 5, 3003;
(f) R. Chun, S. Kim, S. -H. Han, S. Han, S. -H. Lee, N. -K. Mishra, Y.
-H. Jung, H. -S. Kim and I. -S. Kim, Adv. Synth. Catal., 2019, 361,
1617; (g) H. Wang, Y. Huang, X. Dai and F. Shi, Chem. Commun.,
2017, 53, 5542; (h) K. Natte, W. Li, S. Zhou, H. Neumann and X.-
F. Wu, Tetrahedron Lett., 2015, 56, 1118; (i) W. -F. Li and X. -F.
Wu, J. Org. Chem., 2014, 79, 10410.
View Article Online
DOI: 10.1039/D0OB00362J
17 (a) H. Wang, J. Cai, H. Huang and G.-J. Deng, Org. Lett., 2014, 16,
5324; (b) F. Cheng, Y. Peng, J. Wu and G.-J. Deng, Org. Biomol.
Chem., 2016, 14, 2819; (c) X. Cheng, H. Wang, X. Xiao and G.-J.
Deng, Green Chem., 2016, 18, 5773.
18 (a) R. L. Atienza, H. S. Roth and K. A. Scheidt, Chem. Sci.,
2011, 2, 1772; (b) X. Xin, D. Wang, X. Li and B. Wan, Angew.
Chem. Int. Ed., 2012, 51, 1693.
19 N. Zhang, D. Y, W. Wei, L. Yuan, Y. Cao and H. Wang, RSC
Adv., 2015, 5, 37013.
20 P. Qian, M. Bi, J. Su, Z. Zha and Z. Wang, J. Org. Chem., 2016,
81, 4876.
21 Y. Xu, X. Tang, W. Hu, W. Wu and H. Jiang, Green Chem.,
2014, 16, 3720.
22 Y. Fang, M. Yuan, J. Zhang, L. Zhang, X. Jin, R. Li and J. Li,
Tetrahedron Lett., 2016, 57, 1460.
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DOI: 10.1039/D0OB00362J
Base-controlled divergent synthesis of vinyl sulfones from
(benzylsulfonyl)benzenes and paraformaldehyde
Fuhong Xiao,* Yangling Hu, Huawen Huang, Fen Xu,* and Guo-Jun Deng
O O
S
N
Et3
Ar2
Ar1
base
controled
Ar2
S
O O
Ar2
(CH2O)n
Ar1
pyridin
S
O O
Ar1
e
A tuneable metal-free protocol for the selective preparation of α-substituted vinyl
sulfone and (E)-vinyl sulfone derivatives has been described. The base played an
important role in the selectivity control of transformation.