Phosphoric Acid-Mediated Synthesis of Vinyl Sulfones through Decarboxylative Coupling Reactions of Sodium Sulfinates with Phenylpropiolic Acids

Article abstract of DOI:10.1021/acs.joc.5b01212

A novel phosphoric acid -mediated synthesis of vinyl sulfones through decarboxylative coupling reactions of sodium sulfinates with phenylpropiolic acids is described. This transformation is efficient and environmentally friendly.

Full text of DOI:10.1021/acs.joc.5b01212

Article
pubs.acs.org/joc
Phosphoric Acid-Mediated Synthesis of Vinyl Sulfones through
Decarboxylative Coupling Reactions of Sodium Sulfinates with
Phenylpropiolic Acids
Guangwei Rong,† Jincheng Mao,*,†,‡ Hong Yan,† Yang Zheng,† and Guoqi Zhang*,§
†Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science,
Soochow University, Suzhou 215123, P. R. China
‡State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, P. R.
China
§Department of Sciences, John Jay College, and The Graduate Center, The City University of New York, New York, New York
10019, United States
S
* Supporting Information
ABSTRACT: A novel phosphoric acid -mediated synthesis of
vinyl sulfones through decarboxylative coupling reactions of
sodium sulfinates with phenylpropiolic acids is described. This
transformation is efficient and environmentally friendly.
synthesizing vinyl sulfones from terminal epoxides and sodium
sulfinates. However, two regioisomers (both linear and
branched vinyl sulfones) were obtained in most cases.8 Very
recently, significant progress on the green synthesis of vinyl
sulfones was made by Jiang and co-workers, who revealed a
transition metal-free approach via tandem cross decarboxylative
reactions between sodium sulfinates and cinnamic acids.9c In
the past decades, decarboxylative coupling reactions have been
a prominent research topic because they provided straightfor-
ward and efficient pathways to the formation of carbon−carbon
and carbon−heteroatom bonds under relatively mild con-
ditions.10 In this regard, the application of the decarboxylative
coupling method to the synthesis of vinyl sulfones has been
studied little in recent years. Except for the results of Guo and
Jiang mentioned above,9 another work accomplished by the
latter group introduced a new protocol for preparing such
compounds, i.e., a palladium-catalyzed decarboxylative coupling
reaction between propiolic acids and sodium sulfinates.9d
Inspired by these works and our recent success with transition
metal-free synthesis,11 we were dedicated to exploring a greener
and more sustainable approach to the decarboxylative coupling
based upon the same substrates without the use of noble
palladium catalysts. Herein, we report our results on a green,
effective phosphorus acid-mediated synthesis of vinyl sulfones
under catalyst-free conditions (Scheme 1).
INTRODUCTION
■
Vinyl sulfones are important structural units that have received
considerable attention in synthetic chemistry, mainly because
they constitute a significant component in biologically active
compounds1 and also serve as useful chemical intermediates for
synthesis.2 Conventional methods for the synthesis of vinyl
sulfones involve the oxidation of the corresponding sulfides,3 β-
elimination of selenosulfones and halosulfones,4 and addition of
PhSO2X (X = I, Cl, etc.) to alkynes/alkenes.5 In contrast to
known strategies that often require a stoichiometric amount of
metallic reagents and harsh reaction conditions,3−5 transition
metal-catalyzed cross coupling reactions adopt the advantages
of mild conditions, low catalyst loading and good availability of
starting materials, and thus, they have been extensively explored
in recent years. In 1983, Kamigata’s group reported the
reactions of arenesulfonyl chlorides with olefins catalyzed by a
ruthenium(II) complex.6 A high level of conversion of vinyl
sulfones was achieved, while the use of the noble catalyst made
the method less economic. Thereafter, much cheaper and
greener catalysts such as copper complexes were developed by
the research groups of Nair, Taniguchi, Jiang, etc.7 For example,
the Taniguchi group revealed an aerobic copper-catalyzed
synthesis of (E)-alkenyl sulfones via the addition of sodium
sulfinates to alkynes, including internal alkynes that have been
scarcely exploited.7e Recently, Guo’s group explored a copper-
catalyzed aerobic decarboxylative sulfonylation reaction in
which cinnamic acids and sodium sulfinates were chosen as
the starting materials. Further studies of preparing vinyl sulfone
derivatives were focused on more environmentally benign,
operationally simple, and efficient cross coupling strategies.7−9
Such work was conducted by Chutima and Nair’s group by
using alkenes and sodium sulfinates in the presence of a
stoichiometric amount of oxidant and iodine compounds.7 In
2012, Yadava’s group also reported a green method for
RESULTS AND DISCUSSION
■
We initiated the study by reacting phenylpropiolic acid (1a)
with sodium benzenesulfinate (2a) in the presence of a catalytic
amount of CuI (20 mol %) in DMSO at 80 °C for 12 h.
However, no desired product was detected from the reaction
Received: June 2, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 1. Comparison of Our Work with Previous Work on the Synthesis of Vinyl Sulfones
mixture. Next, various additives such as bases and acids were
tested. Although the addition of sodium carbonate as a base did
not promote the reaction, much to our excitement, 23% of 3a
as a desired decarboxylative product was obtained with an
exclusively E isomer when acetic acid was added to the reaction
system. Interestingly, the yield can be further increased to 30%
after the catalyst has been removed. Encouraged by this result,
we examined some different protic acids. Apparently, strong
protic acids, including sulfuric acid and TFA (trifluoroacetic
acid), disfavored the reaction, as do very weak acid like ethanol
(entries 5−7 of Table 1). However, moderate yields were
achieved when several organic acids such as pivalic acid,
malonic acid, and terephthalic acid were used (entries 8−10). It
was pleasing to find that 73% of 3a was isolated when
phosphorus acid was employed in the reaction, and the result
was remarkably improved by increasing the amount of sodium
benzenesulfinate (3.0 equiv), from which a high yield (92%) for
3a was reached (entry 13). The solvent effect was subsequently
evaluated, yet much inferior results were observed when
solvents other than DMSO were used (entries 14−16). It is
worth mentioning that the high yield did not decrease
obviously even if the reaction was conducted under an argon
atmosphere (entry 17).
With the optimized reaction conditions described above in
hand, we next explored the substrate scope that is applicable for
the current reaction. Therefore, a series of substituted aromatic
propiolic acids were introduced to react with sodium
benzenesulfinate. Alkyl-substituted phenylpropiolic acids
tended to afford the corresponding products in high yields
(3a, 3b, and 3d), while a much lower yield of 3c was gained
when the substrate was phenylpropiolic acid bearing an
electron-withdrawing group on the phenyl ring (Table 2). All
reactions proceeded smoothly when para-halogen-substituted
substrates were utilized to react with sodium benzenesulfinate,
affording 3e, 3f, and 3g in 88, 84, and 80% yields, respectively.
Because of the steric hindrance effect of ortho-position
substitution, only 23% of 3i was formed, which is in contrast
with the case for 3h, where the chloro group is located on the
meta position of the phenyl ring. This effect was then confirmed
when comparing the results for products 3l and 3m. It was
found that only a trace amount of 3l was detected for the
reaction involving naphth-1-ylpropiolic acid, whereas naphth-2-
ylpropiolic acid proved to be an excellent substrate, providing
3m in 90% yield. To our delight, substrates such as 2n and 2o
bearing active functional groups (ketone or aldehyde) were also
compatible with the reaction conditions and the corresponding
products 3n and 3o were both isolated in good yields.
To further extend the applications of the reaction presented
here, the substrate scope of sodium sulfinates was investigated
under standard conditions. All reactions that were performed
here afforded the desired vinyl sulfone products in moderate to
good yields; sodium benzenesulfinates having very strong
electron-withdrawing substituents were less effective substrates,
and the yields for 3t and 3u were somewhat lower. Generally,
halogen substitution favored high conversions giving the
expected products in good yields. It was interesting to note
that aliphatic sodium sulfinates, including sodium methane-
sulfinate and sodium ethanesulfinate, were also suitable
substrates for this transformation, generating the corresponding
products 3w and 3x in excellent yields.
Table 1. Condition Optimization of Decarboxylative
Coupling between Phenylpropiolic Acid and Sodium
a
Benzenesulfinate
b
entry
catalyst
additive
solvent
DMSO
yield (%)
1
CuI
CuI
CuI
−
−
−
−
−
−
−
−
−
−
−
−
−
−
−
nd
nd
23
30
nd
nd
nd
34
56
68
73
75
92
82
23
35
91
2
Na2CO3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
CH3CN
1,4-dioxane
DCE
3
HOAc
4
HOAc
5
ethanol
6
H2SO4
7
TFA
8
pivalic acid
malonic acid
terephthalic acid
pyruvic acid
phosphorus acid
phosphorus acid
phosphorus acid
phosphorus acid
phosphorus acid
phosphorus acid
9
10
11
12
c
13
14
15
16
To gain insights into the mechanistic aspect of the reaction,
phenylacetylene was employed to react with sodium
benzenesulfinate under standard conditions. However, an
unexpected product 4 was isolated in 25% yield, instead of
the vinyl sulfone 3a, which indicated the reaction between 1
and 2 did not involve a process in which phenylpropiolic acid
was first converted to phenylacetylene before reacting with
c,d
17
DMSO
a
Reaction conditions: phenylpropiolic acid 1a (0.3 mmol), sodium
benzenesulfinate 2a (2 equiv, 0.6 mmol), catalyst (20 mol %), additive
b
(0.6 mmol), solvent (2 mL), 80 °C, 12 h, air. nd, not detected.
c
d
Sodium benzenesulfinate 2a (3 equiv, 0.9 mmol). Argon
atmosphere.
B
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
a
Table 2. Substrate Scope for the Synthesis of Various Vinyl Sulfones
a
Reaction conditions: aromatic propiolic acid 1 (0.3 mmol), sodium sulfinate (3 equiv, 0.9 mmol), phosphorus acid (0.6 mmol), DMSO (2 mL), 80
°C, 12 h, air.
sodium sulfinate. On the other hand, the reaction of 1a with 2a
was dramatically inhibited while a radical scavenger, 2,2,6,6-
tetramethylpiperidinooxy (TEMPO, 4.0 equiv), was added to
the reaction mixture under standard conditions (Scheme 2, eq
2). This suggests that a radical process was likely to be involved
in the reaction. In addition, sodium phenylpropioate reacted
smoothly with sodium sulfinate under the standard conditions,
although the yield was a little lower (eq 3). Interestingly,
another moderately strong acid, benzenesulfinic acid, was
chosen to replace phosphorus acid for the same reaction, and a
comparable yield was obtained. However, the reaction did not
proceed in the absence of sodium sulfinate 2a (eqs 4 and 5).
Furthermore, the reaction mediated by benzene sulfinic acid
was also conducted by adding 2.0 equiv of D2O, and a
deuterated product 3a′ was observed in approximately 10%
yield, except for the major product 3a (eq 6). According to
these findings, we assume that sodium sulfinate should act as
both a base for the deacrboxylation of phenylpropiolic acid and
the sulfonylating reagent, and phosphorus acid could perform
as a protonating reagent during the reaction.
heating, which could be resonance-stabilized with a sulfonyl
radical B.13 Next, intermediate D was formed through the trans
addition of B to the triple bond of C resulting from the
deprotonation of phenylpropiolic acid in the presence of basic
sodium sulfinate. An anionic E was readily produced after the
removal of one molecule of carbon dioxide from D followed by
the abstraction of a hydrogen radical from phosphoric acid.12 E
was eventually converted to the desired product 3 with the
assistance of phosphoric acid.9c,12e
CONCLUSIONS
■
In summary, we have developed a green and efficient
phosphoric acid-mediated synthesis of vinyl sulfones through
decarboxylative coupling reactions of sodium sulfinates with
phenylpropiolic acids. A broad range of substrates, including
both substituted propiolic acids and sodium sulfinates, were
tolerated with our protocol under optimal conditions, and a
variety of vinyl sulfone products were obtained in moderate to
excellent yields. The synthetic method presented here features
many advantages such as simple operation, catalyst-free and
green reaction conditions, a broad substrate scope, and good
yields, which is promising for practical applications in relevant
industrial and manufacturing processes in the future.
On the basis of the results described above and previous
literature reports,12 a plausible mechanism was proposed in
Scheme 3. An oxygen-centered radical A was initially generated
through the oxidation of sodium sulfinate 2 by DMSO upon
C
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 2. Relevant Experiments for the Mechanistic Studies
Scheme 3. A Plausible Mechanism for the Formation of Product 3
removal of the solvent, the residue was subjected to column
chromatography on silica gel using ethyl acetate/petroleum ether
mixtures to afford the desired product in high purity.
EXPERIMENTAL SECTION
■
General Information. All reactions were conducted under an air
atmosphere. Various phenylpropiolic acids and various sodium
sulfinates were commercially available. The cuprous iodide (99%)
was purchased from known corporations. Flash column chromatog-
raphy was performed using silica gel (100−200 mesh). Analytical thin-
layer chromatography was performed using glass plates precoated with
200−300 mesh silica gel impregnated with a fluorescent indicator (254
nm). NMR spectra were recorded in CDCl3 on a 400 MHz NMR or
300 MHz NMR spectrometer with TMS as an internal reference.
(E)-[2-(Phenylsulfonyl)vinyl]benzene (3a).9c White solid: mp 67−
1
69 °C; yield 92% (67.4 mg); H NMR (400 MHz, CDCl3) δ 7.97−
7.94 (m, 2H), 7.69 (d, J = 15.6 Hz, 1H), 7.64−7.59 (m, 1H), 7.58−
7.52 (m, 2H), 7.50−7.46 (m, 2H), 7.42−7.37 (m, 3H), 6.87 (d, J =
15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 142.0, 140.2,
132.9, 131.9, 130.8, 128.9, 128.6, 128.1, 127.2, 126.8; MS calcd for
C14H12O2S m/z 244.1, found m/z 245.1 (M + H)+.
(E)-1-Methyl-4-[2-(phenylsulfonyl)vinyl]benzene (3b).9c White
Products were characterized by comparison of H NMR, 13C NMR,
MS, and TOF-MS data in the literature.
1
1
solid: mp 130−132 °C; yield 89% (69.0 mg); H NMR (400 MHz,
CDCl3) δ 7.97−7.92 (m, 2H), 7.65 (d, J = 15.6 Hz, 1H), 7.61 (t, J =
7.2 Hz, 1H), 7.54 (t, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 7.18 (d,
J = 8.0 Hz, 2H), 6.81 (d, J = 15.2 Hz, 1H), 2.36 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 142.6, 141.9, 140.9, 133.3, 129.8, 129.6,
129.3, 128.6, 127.6, 126.0, 21.5; MS calcd for C15H14O2S m/z 258.1,
found m/z 259.1 (M + H)+.
General Procedure for the Reaction between Phenyl-
propiolic Acids and Sodium Benzenesulfinate. To a Schlenk
tube equipped with a magnetic stir bar were added phenylpropiolic
acid (0.3 mmol, 43.8 mg), sodium benzenesulfinate (3 equiv, 0.9
mmol, 147.7 mg), phosphoric acid (85 wt % in water, 0.6 mmol, 69.2
mg), and DMSO (2.0 mL). The resulting reaction mixture was stirred
at 80 °C for 12 h. At the end of the reaction, the reaction mixture was
cooled to room temperature amd water (10 mL) was added. The
mixture was then diluted with ethyl acetate (3 × 10 mL). The
combined organic phase was dried over anhydrous Na2SO4. After
(E)-1-[2-(Phenylsulfonyl)vinyl]-4-(trifluoromethyl)benzene (3c).9c
1
White solid: mp 133−135 °C; yield 43% (40.3 mg); H NMR (400
MHz, CDCl3) δ 7.99−7.94 (m, 2H), 7.81 (d, J = 15.6 Hz, 1H), 7.68−
7.63 (m, 3H), 7.62−7.55 (m, 4H), 6.97 (d, J = 15.2 Hz, 1H); 13C{1H}
D
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
NMR (100 MHz, CDCl3) δ 140.4, 140.1, 135.7, 133.7, 132.6 (q, J =
32.7 Hz), 130.0, 129.5, 128.8, 127.8, 126.0 (q, J = 3.7 Hz), 123.6 (d, J
= 270.8 Hz); MS calcd for C15H11F3O2S m/z 312.0, found m/z 313.0
(M + H)+.
(E)-1-{4-[2-(Phenylsulfonyl)vinyl]phenyl}ethanone (3n).14 White
solid: mp 148−150 °C; yield 85% (73.1 mg); H NMR (400 MHz,
1
CDCl3) δ 7.97−7.93 (m, 4H), 7.69 (d, J = 15.5 Hz, 1H), 7.65−7.60
(m, 1H), 7.59−7.53 (m, 4H), 6.96 (d, J = 15.5 Hz, 1H), 2.61−2.58
(m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 197.1, 140.8, 140.2,
138.7, 136.6, 133.7, 129.8, 129.5, 128.9, 128.7, 127.8, 26.7; MS calcd
for C16H14O3S m/z 286.1, found m/z 287.1 (M + H)+.
(E)-1-tert-Butyl-4-[2-(phenylsulfonyl)vinyl]benzene (3d).7c White
1
solid: mp 116−118 °C; yield 78% (70.3 mg); H NMR (400 MHz,
CDCl3) δ 7.97−7.93 (m, 2H), 7.68 (d, J = 15.6 Hz, 1H), 7.63−7.58
(m, 1H), 7.56−7.51 (t, J = 8.0 Hz, 2H), 7.45−7.39 (m, 4H), 6.83 (d, J
= 15.2 Hz, 1H), 1.30 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3) δ
155.0, 142.5, 140.9, 133.3, 129.6, 129.3, 128.5, 127.6, 126.2, 126.1,
35.0, 31.1; MS calcd for C18H20O2S m/z 300.1, found m/z 301.1 (M +
H)+.
(E)-4-[2-(Phenylsulfonyl)vinyl]benzaldehyde (3o).15 White solid:
mp 162−164 °C; yield 82% (67.2 mg); 1H NMR (400 MHz, CDCl3)
δ 10.02 (s, 1H), 7.98−7.93 (m, 2H), 7.89 (d, J = 8.0 Hz, 2H), 7.71 (d,
J = 15.5 Hz, 1H), 7.66−7.61 (m, 3H), 7.59−7.53 (m, 2H), 7.00 (d, J =
15.5 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 190.8, 140.1,
139.6, 137.4, 137.2, 133.3, 130.0, 129.7, 129.0, 128.6, 127.4; MS calcd
for C15H12O3S m/z 272.1, found m/z 273.1 (M + H)+.
(E)-1-Fluoro-4-[2-(phenylsulfonyl)vinyl]benzene (3e).9c White
1
solid: mp 108−110 °C; yield 88% (69.2 mg); H NMR (400 MHz,
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3p).7f White solid: mp
CDCl3) δ 7.95 (d, J = 8.4 Hz, 2H), 7.68−7.60 (m, 2H), 7.58−7.52 (m,
2H), 7.51−7.46 (m, 2H), 7.11−7.04 (m, 2H), 6.82 (dd, J = 15.2, 1.2
Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.3 (d, J = 251.5
Hz), 141.2, 140.6, 133.5, 130.6 (d, J = 8.7 Hz), 129.4, 128.6 (d, J = 3.4
Hz), 127.6, 127.0 (d, J = 2.3 Hz), 116.3 (d, J = 22.0 Hz); MS calcd for
C14H11FO2S m/z 262.0, found m/z 285.0 (M + Na)+.
1
118−120 °C; yield 87% (67.4 mg); H NMR (400 MHz, CDCl3) δ
7.83 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 15.2 Hz, 1H), 7.49−7.44 (m,
2H), 7.41−7.36 (m, 3H), 7.33 (d, J = 8.4 Hz, 2H), 6.86 (d, J = 15.6
Hz, 1H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 144.4,
142.0, 137.7, 132.4, 131.1, 130.0, 129.1, 128.5, 127.7, 127.6, 21.6; MS
calcd for C15H14O2S m/z 258.1, found m/z 259.1 (M + H)+.
(E)-1-Fluoro-4-(styrylsulfonyl)benzene (3q).11b White solid: mp
(E)-1-Chloro-4-[2-(phenylsulfonyl)vinyl]benzene (3f).9c White
1
solid: mp 128−130 °C; yield 84% (70.2 mg); H NMR (400 MHz,
1
CDCl3) δ 7.98−7.93 (m, 2H), 7.66−7.61 (m, 2H), 7.58−7.53 (m,
2H), 7.44−7.40 (m, 2H), 7.38−7.33 (m, 2H), 6.87 (d, J = 15.2 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3) δ 141.0, 140.4, 137.2, 133.6,
130.8, 129.8, 129.4, 129.4, 127.9, 127.7; MS calcd for C14H11ClO2S m/
z 278.0, found m/z 279.0 (M + H)+.
80−82 °C; yield 82% (64.5 mg); H NMR (400 MHz, CDCl3) δ
8.00−7.93 (m, 2H), 7.68 (d, J = 15.6 Hz, 1H), 7.52−7.46 (m, 2H),
7.43−7.37 (m, 3H), 7.25−7.18 (m, 2H), 6.86 (d, J = 15.2 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 165.4 (d, J = 254.5 Hz), 142.5,
136.6 (d, J = 3.1 Hz), 132.0, 131.2, 130.4 (d, J = 9.6 Hz), 129.0, 128.5,
126.9, 116.5 (d, J = 22.5 Hz); MS calcd for C14H11FO2S m/z 262.0,
found m/z 263.0 (M + H)+.
(E)-1-Bromo-4-[2-(phenylsulfonyl)vinyl]benzene (3g).9c White
1
solid: mp 152−154 °C; yield 80% (77.6 mg); H NMR (400 MHz,
CDCl3) δ 7.98−7.92 (m, 2H), 7.66−7.63 (m, 1H), 7.62−7.59 (m,
1H), 7.58−7.53 (m, 2H), 7.53−7.49 (m, 2H), 7.34 (d, J = 8.4 Hz,
2H), 6.88 (d, J = 15.6 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
141.1, 140.4, 133.6, 132.4, 131.3, 130.0, 129.4, 128.0, 127.7, 125.6; MS
calcd for C14H11BrO2S m/z 322.0, found m/z 323.0 (M + H)+.
(E)-1-Chloro-3-[2-(phenylsulfonyl)vinyl]benzene (3h).7f White
(E)-1-Chloro-4-(styrylsulfonyl)benzene (3r).7f White solid: mp 86−
1
88 °C; yield 84% (70.2 mg); H NMR (400 MHz, CDCl3) δ 7.91−
7.86 (m, 2H), 7.69 (d, J = 15.2 Hz, 1H), 7.53−7.46 (m, 4H), 7.44−
7.36 (m, 3H), 6.85 (d, J = 15.6 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 142.6, 139.6, 138.8, 131.7, 130.9, 129.2, 128.7, 128.7, 128.2,
126.4; MS calcd for C14H11ClO2S m/z 278.0, found m/z 279.0 (M +
H)+.
1
solid: mp 98−100 °C; yield 91% (76.1 mg); H NMR (400 MHz,
CDCl3) δ 7.84−7.78 (m, 2H), 7.72−7.65 (m, 3H), 7.51−7.46 (m,
2H), 7.44−7.36 (m, 3H), 6.84 (d, J = 15.2 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 142.6, 139.3, 132.2, 131.7, 131.0, 128.7, 128.7,
128.2, 126.3; MS calcd for C14H11ClO2S m/z 278.0, found m/z 279.0
(M + H)+.
(E)-1-Bromo-4-(styrylsulfonyl)benzene (3s).7f White solid: mp 98−
1
100 °C; yield 83% (80.5 mg); H NMR (400 MHz, CDCl3) δ 7.83−
7.78 (m, 2H), 7.72−7.66 (m, 3H), 7.50−7.46 (m, 2H), 7.44−7.36 (m,
3H), 6.65 (d, J = 15.6 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
143.1, 139.8, 132.7, 132.2, 131.5, 129.2, 129.2, 128.7, 126.8; MS calcd
for C14H11BrO2S m/z 322.0, found m/z 223.0 (M + H)+.
(E)-1-Chloro-2-[2-(phenylsulfonyl)vinyl]benzene (3i).9c White
1
solid: mp 102−104 °C; yield 23% (19.2 mg); H NMR (400 MHz,
(E)-1-Nitro-4-(styrylsulfonyl)benzene (3t).9c White solid: mp 156−
CDCl3) δ 8.09 (d, J = 15.2 Hz, 1H), 8.00−7.95 (m, 2H), 7.67−7.61
(m, 1H), 7.60−7.54 (m, 2H), 7.51 (dd, J = 7.6, 1.6 Hz, 1H), 7.43 (dd,
J = 8.0, 1.2 Hz, 1H), 7.34 (td, J = 7.6, 1.6 Hz, 1H), 7.29−7.24 (m, 1H),
6.90 (d, J = 15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 139.8,
137.9, 134.9, 133.1, 131.4, 130.2, 129.9, 129.6, 128.9, 127.8, 127.4,
126.7; MS calcd for C14H11ClO2S m/z 278.0, found m/z 279.0 (M +
H)+.
1
158 °C; yield 52% (45.1 mg); H NMR (400 MHz, CDCl3) δ 8.41−
8.37 (tt, J = 8.8, 2.4 Hz, 2H), 8.15 (tt, J = 9.2, 2.0 Hz, 2H), 7.77 (d, J =
15.2 Hz, 1H), 7.54−7.49 (m, 2H), 7.48−7.39 (m, 3H), 6.87 (d, J =
15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 150.5, 146.6,
145.0, 131.9, 131.8, 129.3, 129.0, 128.9, 125.7, 124.6; MS calcd for
C14H11NO4S m/z 289.0, found m/z 312.0 (M + Na)+.
(E)-1-(Styrylsulfonyl)-4-(trifluoromethyl)benzene (3u).7f White
(E)-1-Methoxy-4-[2-(phenylsulfonyl)vinyl]benzene (3j).9c White
1
1
solid: mp 125−127 °C; yield 64% (60.0 mg); H NMR (400 MHz,
solid: mp 108−110 °C; yield 38% (31.3 mg); H NMR (400 MHz,
CDCl3) δ 8.09 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.4 Hz, 2H), 7.74 (d, J
= 15.2 Hz, 1H), 7.52−7.48 (m, 2H), 7.46−7.38 (m, 3H), 6.85 (d, J =
15.6 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 144.2, 143.9,
134.8 (q, J = 33.0 Hz), 131.9, 131.5, 129.1, 128.6, 128.1, 126.4 (q, J =
3.7 Hz), 126.1, 123.0 (d, J = 271.4 Hz); MS calcd for C15H11F3O2S m/
z 312.0, found m/z 313.0 (M + H)+.
CDCl3) δ 7.96−7.92 (m, 2H), 7.66−7.58 (m, 2H), 7.56−7.51 (m,
2H), 7.46−7.41 (m, 2H), 6.92−6.88 (m, 2H), 6.71 (d, J = 15.2 Hz,
1H), 3.83 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 162.1, 142.3,
141.1, 133.2, 130.4, 129.3, 127.5, 125.0, 124.4, 114.5, 55.5; MS calcd
for C15H14O3S m/z 274.1, found m/z 275.1 (M + H)+.
(E)-4-[2-(Phenylsulfonyl)vinyl]benzonitrile (3k).7f White solid: mp
(E)-2-(Styrylsulfonyl)naphthalene (3v).11b White solid: mp 138−
140 °C; yield 80% (70.6 mg); 1H NMR (400 MHz, CDCl3) δ 8.56 (d,
J = 1.2 Hz, 1H), 8.02−7.97 (m, 2H), 7.94−7.87 (m, 2H), 7.75 (d, J =
15.2 Hz, 1H), 7.70−7.60 (m, 2H), 7.52−7.47 (m, 2H), 7.43−7.36 (m,
3H), 6.93 (d, J = 15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
142.4, 137.3, 135.0, 132.2, 132.1, 131.1, 129.5, 129.2, 129.1, 129.1,
128.9, 128.4, 127.8, 127.5, 127.1, 122.4; MS calcd for C18H14O2S m/z
294.1, found m/z 295.1 (M + H)+.
1
113−115 °C; yield 87% (70.3 mg); H NMR (400 MHz, CDCl3) δ
7.98−7.94 (m, 2H), 7.71−7.64 (m, 4H), 7.62−7.55 (m, 4H), 6.71 (d, J
= 15.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 139.8, 136.6,
133.9, 132.8, 131.0, 129.6, 129.0, 127.9, 118.1, 114.3; MS calcd for
C15H11NO2S m/z 269.0, found m/z 270.1 (M + H)+.
(E)-2-[2-(Phenylsulfonyl)vinyl]naphthalene (3m).9c White solid:
mp 102−104 °C; yield 90% (79.5 mg); 1H NMR (400 MHz, CDCl3)
δ 8.02−7.97 (m, 2H), 7.90 (s, 1H), 7.87−7.78 (m, 4H), 7.61 (tt, J =
7.2, 2.8 Hz, 1H), 7.58−7.48 (m, 5H), 6.98 (d, J = 15.2 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 142.5, 140.7, 134.4, 133.4, 133.0,
130.9, 129.7, 129.3, 128.9, 128.7, 127.8, 127.6, 127.2, 127.0, 123.4; MS
calcd for C18H14O2S m/z 294.1, found m/z 295.1 (M + H)+.
(E)-[2-(Methylsulfonyl)vinyl]benzene (3w).9c White solid: mp 75−
77 °C; yield 82% (44.8 mg); 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J
= 15.6 Hz, 1H), 7.54−7.50 (m, 2H), 7.46−7.39 (m, 3H), 6.94 (d, J =
15.6 Hz, 1H), 3.04 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
E
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
143.5, 131.6, 130.9, 128.7, 128.1, 125.7, 42.8; MS calcd for C9H10O2S
m/z 182.0, found m/z 183.0 (M + H)+.
39, 5265. (c) Back, T. G.; Collins, S. J. Org. Chem. 1981, 46, 3249.
(d) Nair, V.; Augustine, A.; Panicker, S. B.; Suja, T. D.; Mathai, S. Res.
Chem. Intermed. 2003, 29, 213. (e) Qian, H.; Huang, X. Synlett 2001,
2001, 1913.
(6) Kamigata, N.; Sawada, H.; Kobayashi, M. J. Org. Chem. 1983, 48,
3793.
(7) (a) Katrun, P.; Chiampanichayakul, S.; Korworapan, K.;
Pohmakotr, M.; Reutrakul, V.; Jaipetch, T.; Kuhakarn, C. Eur. J. Org.
Chem. 2010, 2010, 5633. (b) Li, W.; Xu, Y.; Wu, W.; Jiang, C.; Qi, C.;
Jiang, H. Chem. - Eur. J. 2014, 20, 7911. (c) Das, B.; Lingaiah, M.;
Damodar, K.; Bhunia, N. Synthesis 2011, 2011, 2941. (d) Taniguchi, N.
Synlett 2011, 2011, 1308. (e) Taniguchi, N. Tetrahedron 2014, 70,
1984. (f) Wei, W.; Li, J.; Yang, D.; Wen, J.; Jiao, Y.; You, J.; Wang, H.
Org. Biomol. Chem. 2014, 12, 1861. (g) Taniguchi, N. Synlett 2012, 23,
1245.
(E)-[2-(Ethylsulfonyl)vinyl]benzene (3x).9c White solid: mp 66−68
°C; yield 85% (50.0 mg); 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J =
15.2 Hz, 1H), 7.55−7.51 (m, 2H), 7.47−7.41 (m, 3H), 6.82 (d, J =
15.2 Hz, 1H), 3.09 (q, J = 7.6 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 144.7, 131.8, 130.9, 128.7, 128.1,
123.5, 49.0, 6.8; MS calcd for C10H12O2S m/z 196.1, found m/z 219.0
(M + Na)+.
1-Phenyl-2-(phenylsulfonyl)ethanone (4).13d White solid: mp 90−
1
92 °C; yield 25% (19.5 mg); H NMR (400 MHz, CDCl3) δ 7.97−
7.87 (m, 4H), 7.69−7.59 (m, 2H), 7.58−7.52 (t, J = 8.0 Hz, 2H),
7.51−7.45 (t, J = 7.6 Hz, 2H), 4.74 (s, 2H); 13C{1H} NMR (100
MHz, CDCl3) δ 187.5, 138.2, 135.2, 133.9, 133.8, 128.8, 128.7, 128.4,
128.1, 63.0; MS calcd for C14H12O3S m/z 260.1, found m/z 261.1 (M
+ H)+.
(8) Chawla, R.; Kapoor, R.; Singh, A. K.; Yadav, L. D. S. Green Chem.
2012, 14, 1308.
(9) (a) Guo, R.; Gui, Q.; Wang, D.; Tan, Z. Catal. Lett. 2014, 144,
1377. (b) Jiang, Q.; Xu, B.; Jia, J.; Zhao, A.; Zhao, Y.-R.; Li, Y.-Y.; He,
N.-N.; Guo, C.-C. J. Org. Chem. 2014, 79, 7372. (c) Xu, Y.; Tang, X.;
Hu, W.; Wu, W.; Jiang, H. Green Chem. 2014, 16, 3720. (d) Xu, Y.;
Zhao, J.; Tang, X.; Wu, W.; Jiang, H. Adv. Synth. Catal. 2014, 356,
2029.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra for all products. The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/acs.joc.5b01212.
(10) (a) Park, K.; Lee, S. Org. Lett. 2015, 17, 1300. (b) Kan, J.;
Huang, S.; Lin, J.; Zhang, M.; Su, W. Angew. Chem., Int. Ed. 2015, 54,
2199. (c) He, Z.; Qi, X.; Li, S.; Zhao, Y.; Gao, G.; Lan, Y.; Wu, Y.; Lan,
J.; You, J. Angew. Chem., Int. Ed. 2015, 54, 855. (d) Xiong, H.-Y.; Yang,
Z.-Y.; Chen, Z.; Zeng, J.-L.; Nie, J.; Ma, J.-A. Chem. - Eur. J. 2014, 20,
8325. (e) Lang, S. B.; O'Nele, K. M.; Tunge, J. A. J. Am. Chem. Soc.
2014, 136, 13606. (f) Li, X.; Yang, F.; Wu, Y.; Wu, Y. Org. Lett. 2014,
16, 992. (g) Wang, Y.; Li, X.; Leng, F.; Zhu, H.; Li, J.; Zou, D.; Wu, Y.;
Wu, Y. Adv. Synth. Catal. 2014, 356, 3307. (h) Fang, P.; Li, M.; Ge, H.
J. Am. Chem. Soc. 2010, 132, 11898. (i) Sun, C.-L.; Li, H.; Yu, D.-G.;
Yu, M.; Zhou, X.; Lu, X.-Y.; Huang, K.; Zheng, S.-F.; Li, B.-J.; Shi, Z.-J.
Nat. Chem. 2010, 2, 1044.
(11) (a) Rong, G.; Liu, D.; Yan, H.; Chen, J.; Zheng, Y.; Zhang, G.;
Mao, J. Adv. Synth. Catal. 2015, 357, 71. (b) Rong, G.; Mao, J.; Yan,
H.; Zheng, Y.; Zhang, G. J. Org. Chem. 2015, 80, 4697.
(12) (a) Feng, H.; Jia, H.; Sun, Z. J. Org. Chem. 2014, 79, 11812.
(b) Naskar, D.; Roy, S. J. Org. Chem. 1999, 64, 6896. (c) Ranjit, S.;
Duan, Z.; Zhang, P.; Liu, X. Org. Lett. 2010, 12, 4134. (d) Park, K.;
Heo, Y.; Lee, S. Org. Lett. 2013, 15, 3322. (e) Hu, G.; Gao, Y.; Zhao, Y.
Org. Lett. 2014, 16, 4464. (f) Pan, X.; Wan, X.; Yu, X.; Zhang, H.; Xie,
W. Synthesis 2014, 46, 2057.
(13) (a) Narasaka, K.; Mochizuki, T.; Hayakawa, S. Chem. Lett. 1994,
1705. (b) Mochizuki, T.; Hayakawa, S.; Narasaka, K. Bull. Chem. Soc.
Jpn. 1996, 69, 2317. (c) Lu, Q.; Zhang, J.; Wei, F.; Qi, Y.; Wang, H.;
Liu, Z.; Lei, A. Angew. Chem., Int. Ed. 2013, 52, 7156. (d) Lu, Q.;
Zhang, J.; Zhao, G.; Qi, Y.; Wang, H.; Lei, A. J. Am. Chem. Soc. 2013,
135, 11481.
(14) Kabalka, G. W.; Guchhait, S. K. Tetrahedron Lett. 2004, 45,
4021.
(15) Battace, A.; Zair, T.; Doucet, H.; Santelli, M. Synthesis 2006,
2006, 3495.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jcmao@suda.edu.cn. Fax: (+)86-512-65880403.
*E-mail: guzhang@jjay.cuny.edu.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for the grants from the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, State
Education Ministry, the Priority Academic Program Develop-
ment of Jiangsu Higher Education Institutions, and the Key
Laboratory of Organic Synthesis of Jiangsu Province. G.Z.
acknowledges a PSC-CUNY award (67312-0045) from the
City University of New York.
REFERENCES
■
(1) (a) Uttamchandani, M.; Liu, K.; Panicker, R. C.; Yao, S. Q. Chem.
Commun. 2007, 1518. (b) Hof, F.; Schutz, A.; Fah, C.; Meyer, S.; Bur,
D.; Liu, J.; Goldberg, D. E.; Diederich, E. Angew. Chem., Int. Ed. 2006,
45, 2138. (c) Reddick, J. J.; Cheng, J.; Roush, W. R. Org. Lett. 2003, 5,
1967. (d) Wang, G.; Mahesh, U.; Chen, G. Y. J.; Yao, S. Q. Org. Lett.
2003, 5, 737. (e) Meadows, D. C.; Sanchez, T.; Neamati, N.; North, T.
W.; Gervay-Hague, J. Bioorg. Med. Chem. 2007, 15, 1127. (f) Frankel,
B. A.; Bentley, M.; Kruger, R. G.; McCafferty, D. G. J. Am. Chem. Soc.
2004, 126, 3404.
(2) (a) Zhu, Q.; Lu, Y. Org. Lett. 2009, 11, 1721. (b) Noshi, M. N.;
El-awa, A.; Torres, E.; Fuchs, P. L. J. Am. Chem. Soc. 2007, 129, 11242.
(c) Wardrop, D. J.; Fritz, J. Org. Lett. 2006, 8, 3659. (d) Kumamoto,
H.; Deguchi, K.; Wagata, T.; Furuya, Y.; Od-anaka, Y.; Kitade, Y.;
Tanaka, H. Tetrahedron 2009, 65, 8007. (e) Pandey, G.; Tiwari, K. N.;
Puranik, V. G. Org. Lett. 2008, 10, 3611. (f) Clive, D. L. J.; Li, Z.; Yu,
M. J. Org. Chem. 2007, 72, 5608.
(3) (a) Linden, A. A.; Kruger, L.; Backvall, J. J. Org. Chem. 2003, 68,
́
̈
̈
5890. (b) Gelalcha, F. G.; Schulze, B. J. Org. Chem. 2002, 67, 8400.
(c) Matteucci, M.; Bhalay, G.; Bradley, M. Org. Lett. 2003, 5, 235.
(4) (a) Sinnreich, J.; Asscher, M. J. Chem. Soc., Perkin Trans. 1 1972,
1543. (b) Hopkins, P. B.; Fuchs, P. L. J. Org. Chem. 1978, 43, 1208.
(c) Carr, R. V. C.; Williams, R. V.; Paquette, L. A. J. Org. Chem. 1983,
48, 4976. (d) Kroll, F. E. K.; Morphy, R.; Rees, D.; Gani, D.
Tetrahedron Lett. 1997, 38, 8573.
(5) (a) Harwood, L. M.; Julia, M.; Le Thuillier, G. Tetrahedron 1980,
36, 2483. (b) Zhu, S.; Qin, C.; Xu, G.; Chu, Q. Tetrahedron Lett. 1998,
F
DOI: 10.1021/acs.joc.5b01212
J. Org. Chem. XXXX, XXX, XXX−XXX