Aerobic Copper-Catalyzed Synthesis of (E)-Vinyl Sulfones by Direct C-S Bond Oxidative Coupling

Article abstract of DOI:10.1021/acs.joc.9b01400

Copper-catalyzed aerobic oxidative C-S bond coupling reaction between thiophenols and aryl-substituted alkenes for (E)-vinyl sulfones synthesis is reported here. With air utilized as a green oxidant, this transformation not only produces various vinyl sulfones in moderate to good yields but also possesses a simple and ecofriendly system. To clarify the mechanism, kinetic experiments has been investigated.

Full text of DOI:10.1021/acs.joc.9b01400

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Note
Aerobic copper-catalyzed synthesis of (E)-vinyl
sulfones by direct C–S bond oxidative coupling
Xiao Liang, Mingteng Xiong, Heping Zhu, Kexin Shen, and Yuanjiang Pan
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01400 • Publication Date (Web): 16 Jul 2019
Downloaded from pubs.acs.org on July 17, 2019
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Aerobic copper-catalyzed synthesis of (E)-vinyl
sulfones by direct C–S bond oxidative coupling
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Xiao Lianga, Mingteng Xionga, Heping Zhua, Kexin Shenb, Yuanjiang Pana*
a Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, P. R. China 310027
b College of Pharmaceutical Science, Zhejiang University, Hangzhou, Zhejiang, P. R. China
310027
ABSTRACT. Copper-catalyzed aerobic oxidative C–S bond coupling reaction between
thiophenols and aryl substituted alkenes for (E)-vinyl sulfones synthesis is reported here. With
air utilized as green oxidant, this transformation not only produces various vinyl sulfones in
moderate to good yields, but also possesses a simple and eco-friendly system. To clarify the
mechanism, kinetic experiments has been investigated.
Vinyl sulfones are known to be highly versatile building blocks and key structural motifs in the
fields of organic synthesis1 as well as medicinal chemistry.2 Notably, vinyl sulfones are found to
be used in many biological researches as activity-based protein profiling (ABPP) probes and
covalent protease inhibitors.3 Furthermore, it is also discovered as a novel class of
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neuroprotective agents toward Parkinson’s disease therapy.4 The synthetic power of the vinyl
sulfone functional group has been substantially upgraded over the past 30 years. Although
various classic methods to synthesize vinyl sulfones have been established,5-9 the construction of
vinyl sulfones via straightforward cross-coupling to form C–S bond attracted continuous
attention in the recent years. In the reported literatures, common sulfonylation reagents such as
benzenesulfonyl hydrazides, sodium benzenesulfinates, sulfonyl halides, sulfinic acids, and
thiosufonates have been chosen as the sulfonyl donors to form vinyl sulfones. On the other side,
vinyl halides, vinyl triflates, nitro-olefins, alkenylboronic acids, phenylacetylenes,
phenylpropiolic acids, cinnamic acids, epoxides, dibromides, and so on could serve as the
precursor of unsaturated group (Scheme 1).10-14 However, there are still some limitations
presented in the aforementioned transformations, such as toxic and expensive catalysts,
inaccessible starting materials, complicated procedures, low atom economy, and poor selectivity.
Therefore, it is imperative to develop an efficient method fulfilling the demands of green and
sustainable chemistry.
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Scheme 1. Display of building blocks to construct vinyl sulfones
In recent years, oxidative couplings have captured more and more attention because it shows
great potential to provide operationally easy, and highly atom–economic cross–coupling
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strategies for the constitution of natural, biological, pharmaceutical, and material molecules.15
However, owing to traditional oxidants usually possessing high toxicity, risks of explosion, and
difficulty to handle, finding a green and mild oxidant seems to be attractive. Oxygen, as an green
and source-abundant oxidant has been widely applied in the oxidative coupling reactions,16 but
molecular oxygen might decompose the key intermediates along with the process. Therefore,
finding an efficient way to make the air “act correctly” during the catalytic system is of much
importance. In 2017, Wang’s group reported the construction of (E)-vinyl sulfones through
metal-free I2O5-promoted direct oxidative coupling of aromatic alkenes with thiols.12c In 2014,
our group developed the copper-mediated direct S–N bond formation to synthesize sulfonamides
from thiols and formamides via oxygen-activated radical process, during which oxygen acted as
a green oxidant to promote the formation of the sulfonyl group.17a Based on our interest in
copper-oxygen system,17 we wish to construct vinyl sulfones via the direct oxidative of
thiophenol by capturing the oxygen in the air (Scheme 2). Herein, we report an aerobic copper–
catalyzed synthesis of (E)–vinyl sulfones by direct C–S bond oxidative coupling.
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Scheme 2. Strategies for the construction of vinyl sulfones
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To examine the feasibility of the above hypothesis, we commenced our initial trials by using
thiophenols 1a and styrene 2a as model substrates. After screening various reaction parameters,
the target product 3a was isolated in 82% yield under the standard conditions (Table 1, entry 1)
which was finally determined as follows: thiophenol (1a, 0.5 mmol), styrene (2a, 2 equiv), CuI
(Cuprous iodide, 20 mol%), DMAP (N,N-dimethyl-4-aminopyridine, 1 equiv), DMSO/H2O (v/v
= 10 : 1) as solvent; and the reaction was proceeding under open air atmosphere at 80 °C for 10 h
(entry 1, see Table S1 for more screening in the Supporting Information). Conducting this
reaction under N2 atmosphere gave a trace amount of product, while replacing air with O2
decreased the yield (Table 1, entry 2 and 3), implying that styrenes might be over oxidized under
the higher concentration of O2. Thereafter, DMAP showed the best result after checking some
organic and inorganic bases (Table S1, entries 2-7) and we guessed that DMAP might work both
as the base and the ligand to promote the reaction. Furthermore, after surveying the effects of
solvents, we noticed that the mixture of DMSO and H2O was slightly more efficient than pure
DMSO and other common solvents led to sluggish conversion to 3a (Table S1, entries 8-13),
which suggested the addition of water might enhance the solubility of the catalyst. By ultilizing
the oxygen-free solvents and oxygen-free copper salts, the reaction still went smoothly, so we
confirmed that the oxygen source was from air (Table 1, entry 5 and 6). Notably, Cu (I) and Cu
(II) species could both start this reaction (Table 1, entry 11 and 12), suggesting that copper salts
worked as single electron transfer (SET) platform to attend the catalysis. Additionally, no target
product was liberated when using other common catalysts, such as NH4I, I2, Pd(OAc)2, and
Fe(acac)3 (Table 1, entries 9-12). Finally, several additional oxidative additions were tested, such
as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), K2S2O8, and tert-butyl hydroperoxide
(TBHP), but none of them improved the yield (Table S1, entries 28-29).
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Table 1. Optimization of the reaction conditionsa, b
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Entry variations form the standard condition
yield
82
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none
N2 atmosphere
trace
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3
O2 atmosphere
4
pyridine instead of DMAP
Et3N instead of DMAP
CH3CN instead of DMSO/H2O
CuCl2 instead of CuI
CuSCN instead of CuI
NH4I instead of CuI
I2 instead of CuI
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trace
trace
trace
trace
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Fe(acac)3 instead of CuI
Pd(OAc)2 instead of CuI
a
Reaction conditions: 1a (0.5 mmol), 2a (1.0 mmol), catalysts (20 mol%), additives (1 equiv),
solvents (2 mL), stirred at 80 °C for 10 h (open air, operating in Schlenk tubes). b Isolated yields.
Table 2. Substrate scope of thiophenol derivativesa, b
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a
Reaction conditions: 1 (0.5 mmol), 2a (1.0 mmol), CuI (20 mol%), DMAP (1 equiv),
DMSO/H2O (2 mL), stirred at 80 °C for 10 h (open air, operating in Schlenk tubes). b Isolated
yields.
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With the optimal reaction conditions in hand, the substrate scope of the reaction with regard to
thiophenol derivatives 1 and styrene derivatives 2 was explored and the results were summarized
in Table 2 and Table 3. In general, ortho-, meta- and para- substituted thiophenols installing
electron-donating or electron-withdrawing groups on the aromatic ring were compatible with the
standard conditions (Table 2). Particularly, thiophenols with halo-group (3h−3m) and electron-
donating substituents, such as alkyl- (3b−3g) and methoxyl- (3n and 3o) group give higher yields
than those with strong electron-withdrawing substituents (3q and 3r). Furthermore, disubstituted
substrates were also examined, and different dimethyl-compounds and naphthalene-containing
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Table 3. Substrate scope of olefin derivativesa, b
a Reaction conditions: 1a (0.5 mmol), 2 (1.0 mmol), CuI (20 mol%), DMAP (1 equiv),
b
DMSO/H2O (2 mL), stirred at 80 °C for 10 h (open air, operating in Schlenk tubes). Isolated
yields.
compounds could proceed smoothly, giving the corresponding products in moderate yields
(3s−3v). Notably, aliphatic mercaptan, such as 1-butanethiol and 1-hexanethiol also matched this
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catalytic systems, and corresponding products were constructed in moderate yields (3w and 3x).
Unfortunately, pyridinethiol, benzyl mercaptan and 1, 4-benzenedithiol did not work under the
reaction conditions and failed to afford the products. Moreover, the scope of this oxidative
coupling reaction was further developed to various styrene derivatives. To our delight, numerous
substituted styrenes with weak electron-donating groups showed good performance (4a−4i),
whereas stronger electron-donating and electron-withdrawing substituents demonstrated poor
reactivity (4h) and could not start the reactions. Surprisingly, steric hindrance did not
considerably inhibit the transformation, the trisubstituted (4k) and disubstituted (4j) substrates
could afford the corresponding vinyl sulfones in high yields, even aromatic cycloolefin (4l) went
smoothly under the standard condition. However, electron-deficient alkenes, just like
acrylonitrile and ethyl acrylate, preferred to react with olefins to form Michael-addition type
products rather than the target compounds. In addition, aliphatic alkenes, stilbenes, and α-methyl
styrene did not work in the reaction.
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Scheme 3. Control experiments
To clarify the mechanism, several control experiments were conducted. The addition of a radical
scavenger, such as TEMPO, 2,6-di-tert-butyl-4-methylphenol (BHT), or p-benzoquinone (BQ) to
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the standard reaction conditions, would suppress the formation of target compound 3a, which
indicated that a radical pathway was possibly involved during the reaction process (Scheme 3,
entry 1a-1c). Moreover, the target compound was obtained in good yields when using disulfide
5a or thiosulfonate 6a instead of thiophenol 1a as substrates, illustrating 5a and 6a might be the
important intermediates generated during the reaction (Scheme 3, entry 2 and 3). Vinyl sulfide
(7a) could not be oxidized to sulfone under this condition, so the oxidation of thiols must take
place earlier than the cross-coupling of C–S bond (Scheme 3, entry 4). Scale-up experiment
brought a lower but useful yield, up to 65% (Scheme 3, entry 5). Finally, we also checked the
possible side products from the polymerization of styrene, but none of the corresponding peaks
could be found in both NMR and MS spectra.
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Futhermore, kinetic experiments were carried out to detect the distribution of different sulfur-
containing compounds along with the reaction (Figure S3, see Supporting Information). The
results revealed that within the first 1 h of the reaction, thiolphenol 1a was totally oxidized to the
corresponding disulfide 5a. When the reaction time reached 2 h, thiosulfonate 6a, the key
intermediate, which was further oxidized from disulfide was generated. Simultaneously, the
product emerged and gradually accumulated. After 10 h, disulfide along with thiosulfonate were
almost gone, and the yield increased gradually. According to the results, thiosulfonate acted as
the crucial intermediate reacting with styrene to provide sulfonyl group, while the disulfide could
be reproduced from the cleavage of S–S bond of thiosulfonate. Apart from this, a kinetic isotope
effect (KIE) was also examined (Scheme S1). According to results showed before, thiosulfonate
was the true source of sulfonyl group, so it was taken as the reactant to attend this KIE
experiment. Competitive coupling of thiosulfonate with an equimolar mixture of 2a and [D8]-2a
at a lower conversion gave a KIE value of 1.2. Meanwhile, the KIE values (1.0 for 2a) observed
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in parallel reactions suggest that the C–H bond cleavage of 2a was not involved in the rate-
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limiting step.
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Scheme 4. Proposed mechanism
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According to the aforementioned experiments and previous reports,18 a plausible mechanism of
such transformation was proposed in the Scheme 5. Under the standard conditions, 1a was
rapidly oxidized to the corresponding disulfide 5a, followed by further oxidation to form 6a by
capturing oxygen in the air.18d During the tranformation from 5a to 6a, the sulfinyl-Cu(II)
complex underwent S–S bond formation to form the unstable 1,2-disulfoxide which quikly
isomerized to 6a . Subsequently, the cleavage of S–S bond would take place with the existence
of copper salts to release the thiol radical 7 and the sulfonyl radical 8 which would add to the
double bond of 2a to give intermediate 9 and subsequently losing another electron by the
promotion of SET process to give the intermediate 10. Finally, as the proton captured by DMAP
left, target compound was obtained.
In conclusion, we developed a versatile approach for the synthesis of (E)-vinyl sulfones with a
wide range of thiol and vinyl substrates in good yields. Kinetic experiment methods helped in
studying the underlying mechanism, which possibly involved some radical intermediates. The
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synthetic method presented here featured many advantages such as simple starting materials,
green reaction conditions, high selectivity, and excellent atom economy, which was expected to
be used as valuable alternative protocols in corresponding areas. Further studies aimed at
broadening the reaction scope for more suitable substrates are underway in our laboratory.
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EXPERIMENTAL SECTION
General Methods. Unless otherwise noted, all solvents and reagents were commercially
available and used without further purification. All reagents were weighed and handled in air at
room temperature. NMR Spectra were performed at 298K, and all NMR spectra were recorded
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on Bruker AVANCE 400 for H NMR and C{1H} NMR in CDCl3. The NMR chemical shift
1
was reported in ppm relative to 7.26 and 77.20 ppm of CDCl3 solvent as the standards of H
NMR and 13C{1H} NMR. Thin layer chromatography (TLC) employed glass 0.25 mm silica gel
plates. High-resolution mass spectra (HRMS) were tested on SHIMADZU LCMS-IT-TOF,
which was equipped with an electrospray ion source (ESI) operating in positive ion mode.
Melting points were recorded with a micro melting point apparatus and uncorrected. Single
crystal X-ray analysis was conducted on Gemini A Ultra X-ray single crystal diffractometer.
General Procedure for the Synthesis of Sulfones 3a. Under air atmosphere, thiophenol (0.5
mmol, 1a), styrene (1.0 mmol, 2a), cuprous iodide (20 mol%), p-dimethylaminopyridine (1
equiv), in the DMSO/H2O mixtures (v/v = 10/1, 2 mL) were stirred at 80 °C for 10 h in an open
25 mL Schlenk tube (heating mantle as the heat source). After cooling to room temperature, the
mixture was washed with brine and extracted with ethyl acetate. Then the organic layer was
separated and dried over sodium sulfate, which was then evaporated under reduced pressure. The
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residue was separated by column chromatography on silica gel with Petroleum/Ethyl acetate
mixtures (v/v = 10/1) to get the desired product (3a). Such product could be further purified by
means of recrystallization.
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General Procedure for the Synthesis of Thiosulfonate 6a. To a stirred solution of disulfide
(1.09 g, 5.0 mmol) in acetonitrile (10.0 mL) and water (1.0 mL), Selectfluor (4.43 g, 12.5 mmol)
was added at room temperature, and the resulting mixture was stirred. The reaction was
monitored via TLC. After the disulfide disappeared from TLC, the resulting mixture was
extracted with ethyl acetate. Then the organic layer was separated and dried over sodium sulfate,
which was then evaporated under reduced pressure. The residue was separated by column
chromatography on silica gel with Petroleum/Ethyl acetate mixtures (v/v = 5/1) to get the desired
product 6a (1.13 g, 90%) as colorless crystals.
General Procedure for the Synthesis of Vinyl Sulfide 7a. To a flame-dried Schlenk tube with
a magnetic stirring bar was charged with styrene (0.5 mmol), disulfide (0.25 mmol), Cu(OTf)2
(18.1 mg, 0.05 mmol), I2 (127 mg, 0.5 mmol) in DMSO (2 mL) under air atmosphere. The
reaction mixture was stirred at 120 °C until complete consumption of the starting material as
detected by TLC or GC-MS analysis. After the reaction equilibrium, the mixture was poured into
ethyl acetate, which was washed with saturated Na2S2O3 (2 x 15 mL) and then brine (1 x 15 mL).
After the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried
over anhydrous Na2SO4 and evaporated under vacuum. The residue was purified by flash column
chromatography (hexane/ethyl acetate) to afford the desired products 7a as light yellow oil.
General Procedure for the Kinetic Isotope Effect Measurements (Competitive KIE). Under
air atmosphere, thiophenol (0.5 mmol, 1a), styrene (0.5 mmol, 2a), [D8]-styrene (0.5 mmol, [D8]-
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2a), cuprous iodide (20 mol%), p-dimethylaminopyridine (1 equiv), in the DMSO/H2O mixtures
(v/v = 10/1, 2 mL) were stirred at 80 °C for 1 h in an open 25 mL Schlenk tube. After cooling to
room temperature, the mixture was washed with brine and extracted with ethyl acetate. Then the
organic layer was separated and dried over sodium sulfate, which was then evaporated under
reduced pressure. The residue was separated by column chromatography on silica gel with
Petroleum/Ethyl acetate mixtures (v/v = 10/1) to get the mixture (3a and [D7]-3a) in 30% total
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1
yield. A mixture of 3a and [D7]-3a was determined on the basis of H NMR analysis. Based on
the integrations related to different hydrogen resonances, the kinetic isotope effect is calculated
to be kH / kD ≈ 1.2.
General Procedure for the Kinetic Isotope Effect Measurements (Parallel KIE). Under air
atmosphere, thiophenol (0.5 mmol, 1a), styrene (1.0 mmol, 2a) or [D8]-styrene (1.0 mmol, [D8]-
2a), cuprous iodide (20 mol%), p-dimethylaminopyridine (1 equiv), in the DMSO/H2O mixtures
(v/v = 10/1, 2 mL) were stirred at 80 °C for 25, 50, 75, 100 min in four separately open 25 mL
Schlenk tubes and immediately quenched with EtOAc. Next, after cooling to room temperature,
the mixture was washed with brine and extracted with ethyl acetate. Then the organic layer was
separated and dried over sodium sulfate, which was then evaporated under reduced pressure. The
residue was separated by column chromatography on silica gel with Petroleum/Ethyl acetate
mixtures (v/v = 10/1) to get the product in different yields. By plotting the relationship of the
four points, the slope of the line could be calculated. The KIE (for styrene) was determined as kH
/ kD ≈ 1.0.
General Procedure for the Detection the Distrbution for Different Sulfur-containing
Compounds. Under air atmosphere, thiophenol (0.5 mmol, 1a), styrene (1.0 mmol, 2a), cuprous
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iodide (20 mol%), p-dimethylaminopyridine (1 equiv), in the DMSO/H2O mixtures (v/v = 10/1,
2 mL) were stirred at 80 °C for 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 h in ten separately open 25 mL
Schlenk tubes and immediately quenched with EtOAc. Next, after cooling to room temperature,
the mixture was washed with brine and extracted with ethyl acetate. Then the organic layer was
separated and dried over anhydrous Na2SO4, which was then evaporated under reduced pressure.
The residue was separated by column chromatography on silica gel with Petroleum/Ethyl acetate
mixtures (v/v = 10/1) to get the product in different yields.
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(E)-(2-(Phenylsulfonyl)vinyl)benzene (3a). White solid (82% yield, 100.0 mg), m.p. 71-72 °C . 1H
NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.62 (t, J = 7.4
Hz, 1H), 7.55 (t, J = 7.4 Hz, 2H), 7.48 (dd, J = 7.5, 1.9 Hz, 2H), 7.44 – 7.33 (m, 3H), 6.87 (d, J =
15.4 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 142.5, 140.7, 133.4, 132.4, 131.3, 129.4,
129.1, 128.6, 127.7, 127.3. HRMS (ESI, m/z) calcd. for C14H13O2S (M+H)+ 245.0631, found
245.0630.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3b). White solid (69% yield, 89.0 mg), m.p. 119-120 °C
1H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 15.4 Hz, 1H), 7.47 (dd, J =
7.4, 2.0 Hz, 2H), 7.39 (t, J = 5.9 Hz, 3H), 7.34 (d, J = 8.1 Hz, 2H), 6.85 (d, J = 15.4 Hz, 1H),
2.43 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 144.4, 142.0, 137.8, 132.5, 131.1, 130.0, 129.1,
128.54, 127.7, 127.6, 21.6. HRMS (ESI, m/z) calcd. for C15H15O2S (M+H)+ 259.0787, found
259.0790.
(E)-1-Ethyl-4-(styrylsulfonyl)benzene (3c). White solid (62% yield, 84.3 mg), m.p. 101-102 °C .
1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 15.4 Hz, 1H), 7.48 (dd, J =
7.4, 2.0 Hz, 2H), 7.44 – 7.30 (m, 5H), 6.86 (d, J = 15.4 Hz, 1H), 2.72 (q, J = 7.6 Hz, 2H), 1.25 (t,
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J = 7.6 Hz, 3H). C{1H} NMR (101 MHz, CDCl3) δ 150.5, 142.0, 137.9, 132.5, 131.1, 129.1,
128.9, 128.5, 127.8, 127.7, 28.9, 15.2. HRMS (ESI, m/z) calcd. for C16H17O2S (M+H)+ 273.0944,
found 273.0947.
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(E)-1-Isopropyl-4-(styrylsulfonyl)benzene (3d). White solid (62% yield, 88.7 mg), m.p. 99-
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100 °C H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.4 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.48
(dd, J = 7.4, 2.0 Hz, 2H), 7.43 – 7.31 (m, 5H), 6.87 (d, J = 15.4 Hz, 1H), 2.98 (hept, J = 6.9 Hz,
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1H), 1.26 (d, J = 6.9 Hz, 6H). C{1H} NMR (101 MHz, CDCl3) δ 155.1, 142.0, 138.0, 132.5,
131.1, 129.1, 128.6, 127.9, 127.7, 127.5, 34.3, 23.7. HRMS (ESI, m/z) calcd. for C17H19O2S
(M+H)+ 287.1100, found 287.1105.
(E)-1-(tert-Butyl)-4-(styrylsulfonyl)benzene (3e). White solid (73% yield, 109.5 mg), m.p. 112-
113 °C . 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.5 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.55
(d, J = 8.5 Hz, 2H), 7.48 (dd, J = 7.4, 2.0 Hz, 2H), 7.44 – 7.30 (m, 3H), 6.87 (d, J = 15.4 Hz, 1H),
1.33 (s, 9H). 13C{1H} NMR (101 MHz, CDCl3) δ 157.4, 142.0, 137.7, 132.5, 131.1, 129.1, 128.6,
127.7, 127.6, 126.4, 35.3, 31.1. HRMS (ESI, m/z) calcd. for C18H21O2S (M+H)+ 301.1257, found
301.1263.
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(E)-1-Methyl-3-(styrylsulfonyl)benzene (3f). Light yellow oil (74% yield, 95.5 mg). H NMR
(400 MHz, CDCl3) δ 7.75 (t, J = 3.5 Hz, 2H), 7.67 (d, J = 15.4 Hz, 1H), 7.48 (dd, J = 7.5, 2.0 Hz,
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2H), 7.44 – 7.33 (m, 5H), 6.87 (d, J = 15.4 Hz, 1H), 2.43 (s, 3H). C{1H} NMR (101 MHz,
CDCl3) δ 142.3, 140.5, 139.7, 134.2, 132.4, 131.2, 129.3, 129.1, 128.6, 128.0, 127.4, 124.8, 21.4.
HRMS (ESI, m/z) calcd. for C15H15O2S (M+H)+ 259.0787, found 259.0792.
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(E)-1-Methyl-2-(styrylsulfonyl)benzene (3g). Yellow oil (63% yield, 81.3 mg). H NMR (400
MHz, CDCl3) δ 8.11 (dd, J = 7.9, 1.1 Hz, 1H), 7.69 (d, J = 15.4 Hz, 1H), 7.54 – 7.46 (m, 3H),
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7.44 – 7.33 (m, 4H), 7.30 (d, J = 7.5 Hz, 1H), 6.85 (d, J = 15.4 Hz, 1H), 2.64 (s, 3H). C{1H}
NMR (101 MHz, CDCl3) δ 142.9, 138.3, 138.1, 133.7, 132.7, 132.4, 131.3, 129.4, 129.1, 128.6,
126.7, 126.7, 20.4. HRMS (ESI, m/z) calcd. for C15H15O2S (M+H)+ 259.0787, found 259.0788.
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(E)-1-Chloro-4-(styrylsulfonyl)benzene (3h). White solid (81% yield, 112.6 mg), m.p. 82-83 °C .
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.6 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H), 7.54 – 7.46 (m,
4H), 7.45 – 7.33 (m, 3H), 6.86 (d, J = 15.4 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 143.1,
140.1, 139.3, 132.2, 131.5, 129.7, 129.2, 129.2, 128.7, 126.9. HRMS (ESI, m/z) calcd. for
C14H11O2SClNa (M+Na)+ 301.0066, found 301.0061.
(E)-1-Chloro-3-(styrylsulfonyl)benzene (3i). White solid (70% yield, 97.3 mg), m.p. 71-72 °C . 1H
NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.84 (d, J = 7.8 Hz, 1H), 7.70 (d, J = 15.4 Hz, 2H), 7.57
(dd, J = 8.1, 0.8 Hz, 1H), 7.49 (dt, J = 7.6, 3.8 Hz, 3H), 7.46 – 7.34 (m, 3H), 6.87 (d, J = 15.4 Hz,
1H). 13C{1H} NMR (101 MHz, CDCl3) δ 143.5, 142.6, 135.5, 133.6, 132.1, 131.5, 130.7, 129.2,
128.7, 127.7, 126.6, 125.8. HRMS (ESI, m/z) calcd. for C14H11O2SClNa (M+Na)+ 301.0066,
found 301.0060.
(E)-1-Fluoro-4-(styrylsulfonyl)benzene (3j). White solid (55% yield, 72.1 mg), m.p. 79-80 °C . 1H
NMR (400 MHz, CDCl3) δ 8.03 – 7.89 (m, 2H), 7.68 (d, J = 15.4 Hz, 1H), 7.49 (dd, J = 7.6, 1.8
Hz, 2H), 7.46 – 7.34 (m, 3H), 7.22 (t, J = 8.6 Hz, 2H), 6.86 (d, J = 15.4 Hz, 1H). 13C{1H} NMR
(101 MHz, CDCl3) δ 165.6 (d, J = 256.0 Hz), 142.7, 136.8 (d, J = 3.1 Hz), 132.2, 131.4, 130.5 (d,
J = 9.6 Hz), 129.2, 128.6, 127.2, 116.7 (d, J = 22.7 Hz). 19F NMR (376 MHz, CDCl3) δ -103.92 .
HRMS (ESI, m/z) calcd. for C14H12O2FS (M+H)+ 263.0537, found 263.0540.
(E)-1-Bromo-4-(styrylsulfonyl)benzene (3k). White solid (70% yield, 112.7 mg), m.p. 98-100 °C .
1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.7 Hz, 2H), 7.74 – 7.62 (m, 3H), 7.48 (dd, J = 7.6,
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1.7 Hz, 2H), 7.45 – 7.32 (m, 3H), 6.85 (d, J = 15.4 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ
143.1, 139.8, 132.7, 132.2, 131.5, 129.3, 129.2, 128.7, 128.7, 126.8. HRMS (ESI, m/z) calcd. for
C14H11O2BrSNa (M+Na)+ 344.9561, found 344.9556.
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(E)-1-Bromo-3-(styrylsulfonyl)benzene (3l). Yellow oil (48% yield, 77.3 mg). H NMR (400
MHz, CDCl3) δ 8.08 (t, J = 1.8 Hz, 1H), 7.88 (d, J = 7.9 Hz, 1H), 7.76 – 7.65 (m, 2H), 7.49 (dd,
J = 7.6, 1.6 Hz, 2H), 7.46 – 7.35 (m, 4H), 6.86 (d, J = 15.4 Hz, 1H). C{1H} NMR (101 MHz,
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CDCl3) δ 143.6, 142.7, 136.5, 132.1, 131.6, 131.0, 130.5, 129.2, 128.8, 126.6, 126.3, 123.3.
HRMS (ESI, m/z) calcd. for C14H11O2BrSNa (M+Na)+ 344.9561, found 344.9558.
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(E)-1-Fluoro-3-(styrylsulfonyl)benzene (3m). Yellow oil (62% yield, 81.2 mg). H NMR (400
MHz, CDCl3) δ 7.76 (d, J = 7.9 Hz, 1H), 7.71 (d, J = 15.4 Hz, 1H), 7.68 – 7.62 (m, 1H), 7.58 –
7.47 (m, 3H), 7.46 – 7.36 (m, 3H), 7.31 (td, J = 8.3, 2.4 Hz, 1H), 6.88 (d, J = 15.4 Hz, 1H).
13C{1H} NMR (101 MHz, CDCl3) δ 162.5 (d, J = 252.2 Hz), 143.5, 142.9 (d, J = 6.5 Hz), 132.1,
131.5, 131.3 (d, J = 7.7 Hz), 129.2, 128.7, 126.6, 123.5 (d, J = 3.4 Hz), 120.7 (d, J = 21.3 Hz),
115.0 (d, J = 24.3 Hz). 19F NMR (376 MHz, CDCl3) δ -109.05. HRMS (ESI, m/z) calcd. for
C14H12O2FS (M+H)+ 263.0537, found 263.0538.
(E)-1-Methoxy-4-(styrylsulfonyl)benzene (3n). White solid (77% yield, 105.5 mg), m.p. 74-75 °C .
1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 9.0 Hz, 2H), 7.63 (d, J = 15.4 Hz, 1H), 7.47 (dd, J =
7.4, 2.1 Hz, 2H), 7.42 – 7.30 (m, 3H), 7.01 (d, J = 9.0 Hz, 2H), 6.85 (d, J = 15.4 Hz, 1H), 3.87 (s,
3H). 13C{1H} NMR (101 MHz, CDCl3) δ 163.6, 141.4, 132.5, 132.2, 131.1, 129.9, 129.1, 128.5,
127.9, 114.6, 55.7. HRMS (ESI, m/z) calcd. for C15H15O3S (M+H)+ 275.0736, found 275.0739.
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(E)-1-Methoxy-3-(styrylsulfonyl)benzene (3o). Yellow oil (65% yield, 88.9 mg). H NMR (400
MHz, CDCl3) δ 7.67 (d, J = 15.4 Hz, 1H), 7.53 (d, J = 7.7 Hz, 1H), 7.50 – 7.41 (m, 4H), 7.41 –
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7.32 (m, 3H), 7.12 (dd, J = 8.2, 2.5 Hz, 1H), 6.89 (d, J = 15.4 Hz, 1H), 3.85 (s, 3H). C{1H}
NMR (101 MHz, CDCl3) δ 160.1, 142.5, 141.9, 132.4, 131.3, 130.5, 129.1, 128.6, 127.2, 119.9,
112.1, 55.7. HRMS (ESI, m/z) calcd. for C15H15O3S (M+H)+ 275.0736, found 275.0740.
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(E)-N-(4-(Styrylsulfonyl)phenyl)acetamide (3p). White solid (55% yield, 76.8 mg), m.p. 167-
168 °C . 1H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H), 7.84 (d, J = 8.7 Hz, 2H), 7.72 (d, J = 8.7 Hz,
2H), 7.63 (d, J = 15.4 Hz, 1H), 7.50 – 7.44 (m, 2H), 7.44 – 7.33 (m, 3H), 6.85 (d, J = 15.4 Hz,
1H), 2.20 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 169.2, 143.0, 142.2, 134.9, 132.3, 131.29,
129.1, 128.9, 128.6, 127.3, 119.7, 24.7. HRMS (ESI, m/z) calcd. for C16H16NO3S (M+H)+
302.0845, found 302.0850.
(E)-1-(Styrylsulfonyl)-4-(trifluoromethyl)benzene (3q). White solid (49% yield, 76.1 mg), m.p.
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126-127 °C . H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.2 Hz, 2H), 7.81 (d, J = 8.3 Hz, 2H),
7.75 (d, J = 15.4 Hz, 1H), 7.50 (dd, J = 7.8, 1.6 Hz, 2H), 7.47 – 7.36 (m, 3H), 6.87 (d, J = 15.4
Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 144.4, 144.1, 135.0 (q, J = 33.1 Hz), 132.0, 131.7,
129.2, 128.8, 128.3, 126.5 (q, J = 3.7 Hz), 126.3, 123.2 (d, J = 273.1 Hz). 19F NMR (376 MHz,
CDCl3) δ -63.14. HRMS (ESI, m/z) calcd. for C15H11O2F3SNa (M+Na)+ 335.0330, found
335.0326.
(E)-1-Nitro-4-(styrylsulfonyl)benzene (3r). White solid (42% yield, 60.9 mg), m.p. 152-154 °C .
1H NMR (400 MHz, CDCl3) δ 8.39 (d, J = 8.8 Hz, 2H), 8.15 (d, J = 8.8 Hz, 2H), 7.78 (d, J =
15.4 Hz, 1H), 7.56 – 7.49 (m, 2H), 7.49 – 7.37 (m, 3H), 6.86 (d, J = 15.4 Hz, 1H). 13C{1H} NMR
(101 MHz, CDCl3) δ 150.5, 146.6, 145.0, 131.9, 131.8, 129.3, 129.1, 128.9, 125.6, 124.6. HRMS
(ESI, m/z) calcd. for C14H11NO4SNa (M+Na)+ 312.0306, found 312.0300.
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(E)-2,4-Dimethyl-1-(styrylsulfonyl)benzene (3s). Light yellow solid (51% yield, 69.4 mg), m.p.
72-73 °C . 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 15.4 Hz, 1H), 7.48
(dd, J = 7.4, 2.1 Hz, 2H), 7.42 – 7.33 (m, 3H), 7.18 (d, J = 8.1 Hz, 1H), 7.11 (s, 1H), 6.83 (d, J =
15.4 Hz, 1H), 2.59 (s, 3H), 2.38 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 144.5, 142.3, 137.9,
135.4, 133.4, 132.5, 131.1, 129.6, 129.1, 128.5, 127.4, 127.1, 21.4, 20.3. HRMS (ESI, m/z) calcd.
for C16H17O2S (M+H)+ 273.0944, found 273.0947.
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(E)-1,3-Dimethyl-2-(styrylsulfonyl)benzene (3t). White solid (40% yield, 54.4 mg), m.p. 106-
108 °C . 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 15.4 Hz, 1H), 7.49 (dd, J = 7.3, 2.2 Hz, 2H),
7.44 – 7.36 (m, 3H), 7.35 – 7.28 (m, 1H), 7.16 (d, J = 7.6 Hz, 2H), 6.93 (d, J = 15.4 Hz, 1H),
2.72 (s, 6H). 13C{1H} NMR (101 MHz, CDCl3) δ 141.1, 140.0, 136.7, 132.7, 132.5, 131.6, 131.1,
129.1, 128.5, 127.7, 23.1. HRMS (ESI, m/z) calcd. for C16H17O2S (M+H)+ 273.0944, found
273.0947.
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(E)-1-(Styrylsulfonyl)naphthalene (3u). White solid (51% yield, 74.5 mg), m.p. 138-139 °C . H
NMR (400 MHz, CDCl3) δ 8.80 – 8.63 (m, 1H), 8.42 (dd, J = 7.4, 1.0 Hz, 1H), 8.11 (d, J = 8.2
Hz, 1H), 7.94 (d, J = 8.1 Hz, 1H), 7.82 (d, J = 15.4 Hz, 1H), 7.72 – 7.65 (m, 1H), 7.64 – 7.53 (m,
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2H), 7.46 (dd, J = 7.6, 1.7 Hz, 2H), 7.43 – 7.30 (m, 3H), 7.00 (d, J = 15.4 Hz, 1H). C{1H}
NMR (101 MHz, CDCl3) δ 142.7, 135.5, 135.2, 134.2, 132.4, 131.2, 129.9, 129.2, 129.1, 128.7,
128.6, 127.5, 127.0, 124.6, 124.2. HRMS (ESI, m/z) calcd. for C18H15O2S (M+H)+ 295.0787,
found 295.0792.
(E)-2-(Styrylsulfonyl)naphthalene (3v). White solid (78% yield, 114.7 mg), m.p. 133-134 °C . 1H
NMR (400 MHz, CDCl3) δ 8.55 (s, 1H), 7.97 (d, J = 9.0 Hz, 2H), 7.92 – 7.82 (m, 2H), 7.74 (d, J
= 15.4 Hz, 1H), 7.68 – 7.56 (m, 2H), 7.47 (dd, J = 7.5, 1.9 Hz, 2H), 7.42 – 7.30 (m, 3H), 6.93 (d,
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J = 15.4 Hz, 1H). C{1H} NMR (101 MHz, CDCl3) δ 142.6, 137.5, 135.2, 132.4, 132.3, 131.3,
129.7, 129.4, 129.3, 129.2, 129.1, 128.6, 128.0, 127.7, 127.4, 122.6. HRMS (ESI, m/z) calcd. for
C18H15O2S (M+H)+ 295.0787, found 295.0790.
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(E)-(2-(Butylsulfonyl)vinyl)benzene (3w). Light yellow oil (37% yield, 41.4 mg). H NMR (400
MHz, CDCl3) δ 7.60 (d, J = 15.5 Hz, 1H), 7.53 (dd, J = 7.5, 2.0 Hz, 2H), 7.49 – 7.35 (m, 3H),
6.83 (d, J = 15.5 Hz, 1H), 3.17 – 2.84 (m, 2H), 1.92 – 1.68 (m, 2H), 1.47 (dq, J = 14.8, 7.4 Hz,
2H), 0.95 (t, J = 7.4 Hz, 3H). C{1H} NMR (101 MHz, CDCl3) δ 144.8, 132.3, 131.4, 129.2,
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128.6, 124.7, 55.0, 24.6, 21.7, 13.6. HRMS (ESI, m/z) calcd. for C12H17O2S (M+H)+ 225.0944,
found 225.0935.
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(E)-(2-(Hexylsulfonyl)vinyl)benzene (3x). Light yellow oil (41% yield, 51.7 mg). H NMR (400
MHz, CDCl3) δ 7.60 (d, J = 15.5 Hz, 1H), 7.53 (dd, J = 7.4, 2.0 Hz, 2H), 7.49 – 7.37 (m, 3H),
6.82 (d, J = 15.5 Hz, 1H), 3.18 – 2.95 (m, 2H), 1.89 – 1.69 (m, 2H), 1.43 (dt, J = 14.6, 7.2 Hz,
2H), 1.36 – 1.21 (m, 4H), 0.88 (t, J = 6.8 Hz, 3H). C{1H} NMR (101 MHz, CDCl3) δ 144.8,
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131.4, 129.2, 128.6, 124.7, 55.3, 31.2, 28.1, 22.6, 22.3, 13.9. HRMS (ESI, m/z) calcd. for
C14H21O2S (M+H)+ 253.1257, found 253.1254.
(E)-1-Methyl-4-(2-(phenylsulfonyl)vinyl)benzene (4a). White solid (81% yield, 104.5 mg), m.p.
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133-135 °C . H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7.66 (d, J = 15.4 Hz, 1H),
7.63 – 7.57 (m, 1H), 7.57 – 7.50 (m, 2H), 7.37 (d, J = 8.1 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 6.82
(d, J = 15.4 Hz, 1H), 2.36 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 142.6, 141.9, 140.9,
133.3, 129.9, 129.6, 129.3, 128.6, 127.6, 126.1, 21.6. HRMS (ESI, m/z) calcd. for C15H15O2S
(M+H)+ 259.0787, found 259.0788.
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(E)-1-(tert-Butyl)-4-(2-(phenylsulfonyl)vinyl)benzene (4b). White solid (70% yield, 105.0 mg),
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m.p. 107-108 °C . H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.3 Hz, 2H), 7.68 (d, J = 15.4 Hz,
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Hz, 1H), 1.30 (s, 9H). C{1H} NMR (101 MHz, CDCl3) δ 155.0, 142.5, 141.0, 133.3, 129.6,
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129.3, 128.5, 127.6, 126.3, 126.1, 35.0, 31.1. HRMS (ESI, m/z) calcd. for C18H21O2S (M+H)+
301.1257, found 301.1260.
(E)-1-Fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (4c). White solid (69% yield, 90.4 mg), m.p.
106-107 °C . 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.1 Hz, 2H), 7.71 – 7.59 (m, 2H), 7.59 –
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7.52 (m, 2H), 7.52 – 7.45 (m, 2H), 7.08 (t, J = 8.6 Hz, 2H), 6.81 (d, J = 15.4 Hz, 1H). C{1H}
NMR (101 MHz, CDCl3) δ 164.4 (d, J = 253.0 Hz), 141.2, 140.6, 133.5, 130.7, 130.6, 129.4,
128.6 (d, J = 3.3 Hz), 127.7, 127.0 (d, J = 2.3 Hz). 19F NMR (376 MHz, CDCl3) δ -107.68.
HRMS (ESI, m/z) calcd. for C14H12O2FS (M+H)+ 263.0537, found 263.0535.
(E)-1-Bromo-4-(2-(phenylsulfonyl)vinyl)benzene (4d). Light yellow solid (76% yield, 122.4 mg),
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m.p. 150-151 °C . H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.4 Hz, 2H), 7.66 – 7.59 (m, 2H),
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7.54 (dd, J = 19.1, 8.1 Hz, 4H), 7.34 (d, J = 8.5 Hz, 2H), 6.88 (d, J = 15.4 Hz, 1H). C{1H}
NMR (101 MHz, CDCl3) δ 141.1, 140.4, 133.6, 132.4, 131.3, 130.0, 129.4, 128.0, 127.7, 125.7.
HRMS (ESI, m/z) calcd. for C14H12O2BrS (M+H)+ 322.9736, found 322.9742.
(E)-1-Chloro-4-(2-(phenylsulfonyl)vinyl)benzene (4e). White solid (75% yield, 104.3 mg), m.p.
128-130 °C . 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.4 Hz, 2H), 7.71 – 7.59 (m, 2H), 7.55 (t,
J = 7.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 15.4 Hz, 1H).
13C{1H} NMR (101 MHz, CDCl3) δ 141.0, 140.5, 137.3, 133.6, 130.9, 129.8, 129.4, 129.4, 127.9,
127.7. HRMS (ESI, m/z) calcd. for C14H12O2SCl (M+H)+ 279.0241, found 279.0242.
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(E)-1-Chloro-3-(2-(phenylsulfonyl)vinyl)benzene (4f). White solid (84% yield, 116.8 mg), m.p.
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100-102 °C . H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7.67 – 7.59 (m, 2H), 7.56
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(dd, J = 8.2, 6.8 Hz, 2H), 7.46 (s, 1H), 7.40 – 7.29 (m, 3H), 6.89 (d, J = 15.4 Hz, 1H). C{1H}
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NMR (101 MHz, CDCl3) δ 140.8, 140.3, 135.1, 134.2, 133.6, 131.1, 130.4, 129.5, 128.9, 128.2,
127.8, 126.9. HRMS (ESI, m/z) calcd. for C14H12O2SCl (M+H)+ 279.0241, found 279.0244.
(E)-1-Chloro-3-(2-(phenylsulfonyl)vinyl)benzene (4g). White solid (65% yield, 90.4 mg), m.p.
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100-102 °C . H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 15.5 Hz, 1H), 7.97 (d, J = 7.2 Hz, 2H),
7.68 – 7.60 (m, 1H), 7.56 (t, J = 7.5 Hz, 2H), 7.51 (dd, J = 7.8, 1.5 Hz, 1H), 7.42 (dd, J = 8.0, 1.0
Hz, 1H), 7.33 (td, J = 7.7, 1.6 Hz, 1H), 7.30 – 7.22 (m, 1H), 6.91 (d, J = 15.4 Hz, 1H). 13C{1H}
NMR (101 MHz, CDCl3) δ 140.3, 138.4, 135.3, 133.6, 132.0, 130.7, 130.4, 130.1, 129.4, 128.3,
127.8, 127.3. HRMS (ESI, m/z) calcd. for C14H12O2SCl (M+H)+ 279.0241, found 279.0246.
(E)-1-Methoxy-4-(2-(phenylsulfonyl)vinyl)benzene (4h). White solid (51% yield, 69.9 mg), m.p.
107-108 °C . 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.1 Hz, 2H), 7.62 (dd, J = 16.3, 11.3 Hz,
2H), 7.54 (dd, J = 8.2, 6.7 Hz, 2H), 7.43 (d, J = 8.8 Hz, 2H), 6.90 (d, J = 8.8 Hz, 2H), 6.72 (d, J
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= 15.3 Hz, 1H), 3.83 (s, 3H). C{1H} NMR (101 MHz, CDCl3) δ 162.1, 142.3, 141.2, 133.2,
130.4, 129.3, 127.5, 125.0, 124.4, 114.5, 55.5. HRMS (ESI, m/z) calcd. for C15H15O3S (M+H)+
275.0736, found 275.0734.
(E)-4-(2-(Phenylsulfonyl)vinyl)benzonitrile (4i). Light yellow solid (77% yield, 104.0 mg), m.p.
186-188 °C . 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.3 Hz, 2H), 7.74 – 7.63 (m, 4H), 7.63 –
7.53 (m, 4H), 7.01 (d, J = 15.5 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 139.9, 139.8, 136.6,
133.9, 132.8, 131.0, 129.6, 129.0, 127.9, 118.1, 114.3. HRMS (ESI, m/z) calcd. for
C15H11NO2SNa (M+Na)+ 292.0408, found 292.0395.
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(E)-2-(2-(Phenylsulfonyl)vinyl)naphthalene (4j). Light yellow solid (70% yield, 102.9 mg), m.p.
97-98 °C . 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 7.1 Hz, 2H), 7.91 (s, 1H), 7.87 – 7.76 (m,
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4H), 7.64 – 7.58 (m, 1H), 7.58 – 7.46 (m, 5H), 6.97 (d, J = 15.4 Hz, 1H). C{1H} NMR (101
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MHz, CDCl3) δ 142.6, 140.8, 134.5, 133.4, 133.1, 131.0, 129.8, 129.4, 129.0, 128.7, 127.9,
127.7, 127.3, 127.0, 123.5. HRMS (ESI, m/z) calcd. for C18H15O2S (M+H)+ 295.0787, found
295.0792.
(E)-1,3,5-Trimethyl-2-(2-(phenylsulfonyl)vinyl)benzene (4k). White solid (79% yield, 113.0 mg),
1
m.p. 116-117 °C . H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7.87 (d, J = 15.8 Hz,
1H), 7.67 – 7.58 (m, 1H), 7.56 (dd, J = 8.1, 6.7 Hz, 2H), 6.88 (s, 2H), 6.54 (d, J = 15.8 Hz, 1H),
2.29 (s, 6H), 2.27 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 140.9, 140.9, 139.5, 137.2, 133.3,
131.6, 129.5, 129.4, 128.5, 127.6, 21.1, 21.1. HRMS (ESI, m/z) calcd. for C17H19O2S (M+H)+
287.1100, found 287.1103.
3-(Phenylsulfonyl)-1,2-dihydronaphthalene (4l). White solid (45% yield, 60.8 mg), m.p. 122-
123 °C . 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 7.1 Hz, 2H), 7.64 – 7.57 (m, 2H), 7.53 (dd, J
= 8.2, 6.8 Hz, 2H), 7.31 – 7.20 (m, 3H), 7.12 (d, J = 7.0 Hz, 1H), 2.86 (t, J = 8.3 Hz, 2H), 2.50
13
(td, J = 8.3, 1.2 Hz, 2H). C{1H} NMR (101 MHz, CDCl3) δ 139.6, 138.2, 135.6, 135.3, 133.4,
131.0, 130.5, 129.3, 129.1, 128.0, 127.8, 127.2, 27.6, 21.7. HRMS (ESI, m/z) calcd. for
C16H15O2S (M+H)+ 271.0793, found 271.0790.
ASSOCIATED CONTENT
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Supporting Information.
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The Supporting Information is available free of charge on the ACS Publications website at DOI:
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X-ray structural details, mechanism studies, and copies of NMR spectra (PDF)
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X-ray crystallography data for compound 3v (CIF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: panyuanjiang@zju.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foundation of China (No. 21532005)
and the National Key R&D Program of China (No. 2016YFF0200503).
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