Metal-free Oxidative Coupling of Aromatic Alkenes with Thiols Leading to (E)-Vinyl Sulfones

Article abstract of DOI:10.1021/acs.joc.7b00994

A facile I₂O₅-mediated direct oxidative coupling of aromatic alkenes with thiols toward vinyl sulfones has been developed under metal-free conditions. This methodology provides a convenient and efficient approach to various (E)-vinyl sulfones from readily available starting materials with excellent regioselectivity. The present oxidative coupling reaction, not only expands the scope of functionalization of alkenes with thiols, but also makes it a practical and powerful complement to traditional methods for the synthesis of (E)-vinyl sulfones.

Full text of DOI:10.1021/acs.joc.7b00994

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Article
Metal-free Oxidative Coupling of Aromatic
Alkenes with Thiols Leading to (E)-Vinyl sulfones
Leilei Wang, Huilan Yue, Daoshan Yang, Huanhuan Cui,
Minghui Zhu, Jinming Wang, Wei Wei, and Hua Wang
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 09 Jun 2017
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Metal-free Oxidative Coupling of Aromatic Alkenes with
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Thiols Leading to (E)-Vinyl sulfones
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Leilei Wang,†§ Huilan Yue,‡§ Daoshan Yang,† Huanhuan Cui,† Minghui Zhu,†
Jinming Wang,† Wei Wei,†* Hua Wang†*
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†Institute of Medicine and Material Applied Technologies, Key Laboratory of
Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry
and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, China.
‡Key Laboratory of Tibetan Medicine Research, Northwest Institute of Plateau
Biology, Chinese Academy of Sciences, Qinghai 810008, China.
§These authors contributed equally to this work.
∗Corresponding author. Eꢀmail: weiweiqfnu@163.com; huawang_qfnu@126.com.
ABSTRACT: A facile I2O5ꢀmediated direct oxidative coupling of aromatic alkenes
with thiols toward vinyl sulfones has been developed under metalꢀfree conditions.
This methodology provides a convenient and efficient approach to various (E)ꢀvinyl
sulfones from readilyꢀavailable starting materials with excellent regioselectivity. The
present oxidative coupling reaction, not only expands the scope of functionalization of
alkenes with thiols, but also makes it a practical and powerful complement to
traditional methods for the synthesis of (E)ꢀvinyl sulfones.
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INTRODUCTION
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Sulfurꢀcontaining compounds are an important class of chemicals that have wide
applications in the field of organic synthesis,1 materials science,2 and medicinal
chemistry.3 Thus, the development of convenient and efficient method for the
construction of CꢀS bond has attracted the increasing synthetic pursuit of chemists in
both academic and industrial communities.4 In this context, the functionalization of
alkenes with thiols represents one of most straightforward and fascinating protocol to
access various organosulfur compounds.5ꢀ10 Over the past decades, some sulfurꢀ
containing products such as thioethers,5 sulfoxides,6 βꢀacetamido sulfides,7 βꢀoxy
sulfoxides,8 βꢀhydroxy sulfides and sulfoxides,9 and βꢀketosulfones10 have been
successfully prepared via the direct addition reaction of alkenes with thiols (Scheme
1). Despite the significance of these functionalization reactions, it is still an attractive
but challenging task to develop novel, efficient, and especially, environmentally
benign methods to construct other important functional sulfur compounds through
direct functionalization of alkenes with thiols. Recently, iodine pentoxide (I2O5) as
safe and reliable singleꢀelectron oxidative surrogates have been increasingly utilized
for various synthetically useful transformations because of their ready availability,
stability, and low toxicity.11 As part of our continued interest in the construction of
sulfurꢀcontaining compounds,12 here, we wish to report a new and facile I2O5ꢀ
mediated direct oxidative coupling of alkenes with thiols toward (E)ꢀvinyl sulfones
under metalꢀfree conditions (Scheme 1).
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O
Previous work (Addition reaction):
HN
R1
R4
S
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R3
R2
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O
S
O
(O)1,2
0,1
R2
S
+ R3 SH
R1
R3
R1
R3
R1
R2
R2
O(H)
R2
S
R1
R3
This work (Oxidative coupling reaction):
O
R3
I2O5 (1.2 equiv)
S
R2
R3 SH
R1
+
R1
O
DBU (1 equiv)
R2
THF (80 oC), 12h
H
Scheme 1. Methods for the functionalization of alkenes with thiols.
Vinyl sulfones as an important class of sulfurꢀcontaining compounds play a
significant role in pharmaceutical and material sciences.13 In particular, they can serve
as the versatile building blocks to access various useful compounds through a number
of organic transformations.14 The traditional methods to prepare vinyl sulfones are
based on the Knoevenagel condensation of aromatic aldehydes with sulfonylacetic
acids,15 Horner–Emmons reaction of carbonyl compounds with sulfonyl
phosphoranes,16 and Wittig reaction.17 Recently, a series of alternative methods for
vinyl sulfones synthesis have also been developed such as transitionꢀmetalꢀcatalyzed
the crossꢀcoupling of sulfinate salts with vinyl bromides, vinyl triflates, or vinyl
boronic acids,18 the oxidation of preformed vinyl sulfides with stoichiometric
oxidants,19 the coupling reactions of alkenes or cinnamic acids with sulfonyl halides
,
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sodium sulfinates, and sulfonyl hydrazides,20 and the addition of sulfinic acids,
sodium sulfinates, sulfonyl hydrazides, or dimethyl sulfoxide to alkynes.21
Nevertheless, most of these reactions might suffer from some limitations such as the
need of inaccessible starting materials, tedious procedures, harsh reaction conditions,
low atom economy, and poor regioselectivity or toxic metal catalysts. Therefore, it
still remains an attractive task to develop more economic, efficient, and highly
selective methods to access vinyl sulfones under metalꢀfree conditions. The present
protocol of I2O5ꢀmediated direct oxidative coupling alkenes with thiols provides a
facile and efficient approach to various (E)ꢀvinyl sulfones in moderate to good yields
from simple and commercially available starting materials with high regioselectivity,
and does not require the use of any metalꢀcatalysts.
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RESULTS AND DISCUSSION
Initially, styrene (1a) and 4ꢀmethylbenzenethiol (2a) were selected as the model
substrates to optimize various reaction conditions. As shown in Table 1, none of
desired product 3aa was obtained when the model reaction was performed at room
temperature in the presence of I2O5/DBU system (entry 1). To our delight, the yield of
desired vinyl sulfone 3aa was largely improved along with the increasing of the
reaction temperature, and the highest yield (55%) of 3aa was obtained at 80oC in
CH3CN (entry 4). Subsequently, the screening of a range of solvents demonstrated
that the reaction performed in THF was significantly better than those conducted in
1,4ꢀdioxane, DME, DMSO, DMF, EtOH and H2O (entries 4ꢀ10). Further optimization
of various bases showed that DBU was the best choice. Only a trace amount of
product or no product was detected when other bases such as K2CO3, KOH, KOtBu
and Et3N were employed (entries 11ꢀ14). The yield of 3a obviously declined with the
decreasing of DBU loading to 0.5 equiv (entry 15) and no conversion was observed in
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the absence of DBU (entry 16). Next, the investigation on the effect of I2O5 loading
found that the best yield (87%) was obtained when 1.2 equiv of I2O5 was used in the
present reaction system (entry 17). Moreover, no conversion was observed when the
reaction was performed without I2O5 (entry 18).
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Table 1 Optimization of the reaction conditionsa
Entry
1
Base (equiv)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
DBU (1)
K2CO3 (1)
KOH (1)
KOtBu (1)
Et3N (1)
DBU (0.5)
ꢀꢀ
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
1,4ꢀdioxane
DME
T (oC)
25
50
60
80
80
80
80
80
80
80
80
80
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80
80
80
80
80
Yield (%)b
0
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63
75
58
43
21
0
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4
5
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7
THF
8
DMSO
DMF
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12
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EtOH
H2O
THF
trace
0
THF
THF
0
THF
0
THF
49
0
THF
DBU (1)
THF
87c
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DBU (1)
THF
80
0d
a Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), I2O5 (1 equiv), Base (0ꢀ1 equiv), Solvent (2
mL), 50ꢀ80°C, 12 h. b Yields based on 1a. c I2O5 (1.2 equiv). d without of I2O5.
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Under the established reaction conditions, the scope of the I2O5ꢀmediated
oxidative coupling of alkenes with thiols for the construction of (E)ꢀvinyl sulfones
was explored, with the results summarized in Table 2. In general, the reactions of
styrene with various aryl thiols bearing electronꢀrich or electronꢀpoor groups on the
aryl rings gave the corresponding products 3aaꢀ3am in moderate to good yields. It
was found that halogen substituents such as Br, Cl, and F were all well tolerated,
which made this protocol more useful for further structural modification (3ag-3al). 2ꢀ
Naphthalenethiol and heterocycle arylthiols such as pyridineꢀ4ꢀthiol and pyridineꢀ2ꢀ
thiol were also compatible with this process, leading to the expected products 3an-
3ap in moderate yields. It is noteworthy that alkyl thiols with long aliphatic chains
such as butaneꢀ1ꢀthiol and heptaneꢀ1ꢀthiol could also be used in the reactions to give
the corresponding products 3aq and 3ar in moderate yields. The scope of this
oxidative coupling reaction was further expanded to a variety of alkenes. Aromatic
alkenes with electronꢀdonating substituents and with electronꢀwithdrawing
substituents were all tolerated under the standard reaction conditions (3ba–3ga). As
expected, 2ꢀvinylnaphthalene and heterocycle alkene such as 2ꢀvinylpyridine could
also be unambiguously converted into the desired products 3ha and 3ia in 78% and
82% yields, respectively. It should be noted that internal aromatic alkenes (i.e., (E)ꢀ
propꢀ1ꢀenylbenzene and 1,2ꢀdihydronaphthalene) were also suitable substrates,
generating the corresponding products 3ja and 3ka in 44% and 65% yields,
respectively. Nevertheless, when aliphatic alkene such as hexꢀ1ꢀene was employed in
the present reaction system, and the corresponding product 3la was obtained in
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relatively low yield. In addition, methyl acrylate and (E)ꢀmethyl butꢀ2ꢀenoate could
also be used in this transformation to produce the desired products (3ma and 3na) in
40% and 34% yields, respectively. Unfortunately, none of the desired product 3oa was
detected when the reaction of stilbene with 4ꢀmethylbenzenethiol was conducted
under the standard conditions.
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Table 2. Results for the I2O5ꢀmediated oxidative coupling of alkenes with thiols
leading to (E)-vinyl sulfonesa,b
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O
S
O
S
O
S
O
O
O
3ab (91%)
3aa (87%)
3ac (73%)
7
OMe
OMe
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9
O
S
O
S
O
S
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O
O
O
3ad (56%)
3ae (72%)
3af (94%)
Cl
Br
O
S
O
O
S
Cl
F
S
O
O
O
3ah (91%)
3ai (88%)
3ag (90%)
Cl
O
S
O
S
O
S
O
O
O
Cl
Cl
3al (86%)
3ak (87%)
3aj (83%)
N
O
S
O
S
O
S
O
O
O
CF3
3ao (53%)
3am (84%)
3an (58%)
O
S
O
S
O
S
N
O
O
O
3ar (40%)
3aq (43%)
3ap (36%)
O
S
O
S
O
S
O
O
O
F
3ca (81%)
3da (84%)
3ba (79%)
O
S
O
S
O
S
O2N
O
O
O
Cl
Br
3ea (80%)
3ga (48%)
3fa (72%)
O
S
O
S
O
S
O
O
O
N
3ja (44%)
3ia (82%)
3ha (78%)
O
O
S
O
S
O
S
O
MeO
O
O
3la (23%)
3ka (65%)
3ma (40%)
O
O
S
O
S
MeO
Ph
O
O
Ph
3oa (0%)
3na (34%)
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a
Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), I2O5 (0.24 mmol), THF (2 mL), 80oC, 12 h. b
Yields based on 1.
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Furthermore, to demonstrate the efficiency and practicality of this transformation,
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a scaled up reaction was conducted between styrene (1a) and 4ꢀmethylbenzenethiol
(2a) under the standard conditions. As shown in Scheme 2, the gramꢀscale synthesis
of (E)ꢀvinyl sulfone 3aa was achieved in 80% yield without the significant loss of its
efficiency. This result indicates that the present method should be employed as the
practical protocol for a large scale synthesis of (E)ꢀvinyl sulfones.
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Scheme 2. The gram scale reaction
In order to gain some further insights into the reaction mechanism, several
control experiments were carried out (Scheme 3). Initially, the pꢀtolyl 4ꢀ
methylbenzenesulfonothioate (5a) was isolated in 82% yield when the reaction of 4ꢀ
methylbenzenethiol (2a) with I2O5 was conducted for 12h in the absence of styrene
and DBU (Scheme 3 (a)). Furthermore, 1,2ꢀdipꢀtolyldisulfane (4a) was isolated in
24% yield along with pꢀtolyl 4ꢀmethylbenzenesulfonothioate 5a (56%) when the
reaction of 4ꢀmethylbenzenethiol (2a) with I2O5 was conducted for 1h (Scheme 3 (b)).
Then, the interaction of 1,2ꢀdipꢀtolyldisulfane (4a) with I2O5 gave pꢀtolyl 4ꢀ
methylbenzenesulfonothioate (5a) in 58% yield, suggesting that pꢀtolyl 4ꢀ
methylbenzenesulfonothioate (5a) might be generated from the oxidation of 1,2ꢀdipꢀ
tolyldisulfane (4a) (Scheme 3 (c)). Next, we checked the role of pꢀtolyl 4ꢀ
methylbenzenesulfonothioate (5a) in the formation of product 3aa. As shown in
Scheme 3 (d), the desired product 3aa was obtained in 75% yield when the reaction of
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styrene (1a) and pꢀtolyl 4ꢀmethylbenzenesulfonothioate (5a) was conducted under the
standard conditions. Moreover, styrene (1a) reacted with sulfonyl iodide (6a) would
lead to the formation of 3aa in 83% yield in the presence of DBU (Scheme 3 (e)). The
above results indicated that benzenesulfonothioate and sulfonyl iodide might be the
key intermediates in the present reaction system. In addition, the model reaction of 1a
and 2a was extremely inhibited by the addition of radical scavenge 2,2,6,6ꢀ
tetramethylꢀ1ꢀpiperidinyloxy (TEMPO) and TEMPOꢀtrapped thiyl radical complex
(pꢀMePhS–TEMPO) was detected by LCꢀMS experiment (see Supporting
information), suggesting that the present reaction might proceed via a proposed
radical pathway (Scheme 3 (f)).
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Scheme 3. Control Experiments
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Based on the above the experimental results and previous reports,20,22,23
a
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possible reaction pathway was proposed as shown in Scheme 4. Initially, thiyl radical
was generated from the oxidation of thiophenol 2.22a, Subsequently, the dimerization
of thiyl radical generated disulfide 4,22b which was further oxidized by I2O5 would
produce benzenesulfonothioate 5 with the concomitant formation of molecular
iodine.22 Then, the interaction of benzenesulfonothioate 5 with iodine gave the
sulfonyl iodide 6. Next, the addition of sulfonyl iodide 6 to alkene 1 afforded βꢀiodo
sulfone 7. Finally, the elimination of HI from βꢀiodo sulfone with the assistance of
DBU provided the desired product 3.20a,d,23
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Scheme 4. Postulated reaction pathway.
CONCLUSIONS
In summary, a novel and facile method has been successfully developed for the
construction of (E)ꢀvinyl sulfones through metalꢀfree I2O5ꢀpromoted direct oxidative
coupling of aromatic alkenes with thiols. Some notable features can be obtained for
this reaction such as operation simplicity, ready availability of starting materials,
metalꢀfree, oxidant of low toxicity, and high regioꢀ and stereoselectivity, thus making
it a practical and powerful complement to traditional methods for the construction of
(E)ꢀvinyl sulfones.
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EXPERIMENTAL SECTION
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General.
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Chemicals were commercially available and were used without further purification
unless otherwise stated. All solvents were used as received without further
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1
purification unless otherwise stated. H NMR and 13C{1H}NMR spectra were
obtained in CDCl3 with TMS as internal standard (500 MHz 1H and 125 MHz 13C) at
room temperature, the chemical shifts (δ) were expressed in ppm and J values were
given in Hz. The following abbreviations are used to indicate the multiplicity: singlet
(s), doublet (d), triplet (t), quartet (q), doublet of doublets (dd), doublet of triplets (dt),
doublet of quartets (dq) and multiplet (m). All first order splitting patterns were
assigned on the basis of the appearance of the multiplet. Splitting patterns that could
not be easily interpreted were designated as multiplet (m). In a few cases the number
of signals in the 13C NMR spectrum is than due, which may be caused by the
superimposition of signals. HRMS data were obtained by ESI on a TOF mass analyzer.
Column chromatography was performed on silica gel (100ꢀ200 mesh).
General experimental procedure.
In a tube (25 mL), alkene 1 (0.2 mmol), thiol 2 (0.4 mmol), I2O5 (0.24 mmol,
80.1 mg), DBU (0.2 mmol, 30 ꢁL), and THF (2 mL) were added. Then, the tube was
sealed and the reaction vessel was allowed to stir at 80 oC for 12 h. After the reaction,
the solvent was removed under vacuum. The residue was purified by flash column
chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give
the desired product 3.
Gram-scale reaction. In a tube (100 ml), styrene (10 mmol, 1.15 mL), 4ꢀ
methylbenzenethiol (20 mmol, 2.5 g), I2O5 (12 mmol, 4.0 g), DBU (10 mmol, 1.5 mL)
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and THF (20 mL) were added. Then, the tube was sealed and the reaction vessel was
allowed to stir at 80 °C for 12h. After the reaction, the resulting mixture was
concentrated under vacuum and the residue was purified by flash column
chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give
the desired product 3aa in 80% yield (2.06 g).
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The reaction of 4-methylbenzenethiol (2a) with I2O5 (12h). In a seal tube (15
mL), 4ꢀmethylbenzenethiol 2a (0.4 mmol, 49.6 mg), I2O5 (0.24 mmol, 80.1 mg), and
THF (2 mL) were added. Then, the tube was sealed and the reaction vessel was
allowed to stir at 80 °C for 12h. After the reaction, the solution was concentrated in
vacuum, the product 5a was isolated in 82% yield (45.6 mg).
The reaction of 4-methylbenzenethiol (2a) with I2O5 (1h). In a seal tube (15 mL),
4ꢀmethylbenzenethiol 2a (0.4 mmol, 49.6 mg), I2O5 (0.24 mmol, 80.1 mg), and THF
(2 mL) were added. Then, the tube was sealed and the reaction vessel was allowed to
stir at 80 °C for 1h. After the reaction, the solution was concentrated in vacuum, the
product 4a and 5a were isolated in 24% (11.8 mg) and 56% (31.1 mg) yields,
respectively.
The reaction of 1,2-dip-tolyldisulfane (4a) with I2O5. In a seal tube (15 mL), 1,2ꢀ
dipꢀtolyldisulfane (4a) (0.2 mmol, 49.2 mg), I2O5 (0.24 mmol, 80.1 mg), and THF (2
mL) were added. Then, the tube was sealed and the reaction vessel was allowed to stir
at 80 °C for 12h. After the reaction, the solution was concentrated in vacuum, the
product 5a were isolated in 58% yield (32.2 mg).
The reaction of styrene (1a) and p-tolyl 4-methylbenzenesulfonothioate (5a)
under standard conditions. In a seal tube (15 mL), styrene (0.2 mmol, 23ꢁL), pꢀtolyl
4ꢀmethylbenzenesulfonothioate (0.2 mmol, 55.6 mg), I2O5 (0.24 mmol, 80.1 mg),
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DBU (0.2 mmol, 30 ꢁL) and THF (2 mL) were added. Then, the tube was sealed and
the reaction vessel was allowed to stir at 80 °C for 12h. After the reaction, the
resulting mixture was concentrated under vacuum and the residue was purified by
flash column chromatography using a mixture of petroleum ether and ethyl acetate as
eluent to give the desired product 3aa in 75% yield (38.7 mg).
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The reaction of styrene (1a) with sulfonyl iodide (6a) in the presence of DBU. In a
seal tube (15 mL), styrene (0.2 mmol, 23ꢁL), 4ꢀmethylbenzeneꢀ1ꢀsulfonyl iodide (0.4
mmol, 112.8 mg), DBU (0.2 mmol, 30 ꢁL) and THF (2 mL) were added. The reaction
vessel was allowed to stir at 80 °C for 12h. After the reaction, the resulting mixture
was concentrated under vacuum and the residue was purified by flash column
chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give
the desired product 3aa in 83% yield (42.8 mg).
Radical trapping experiment with TEMPO. In a seal tube (15 mL), styrene (0.2
mmol, 23 ꢁL), 4ꢀmethylbenzenethiol (0.4 mmol, 49.6 mg), TEMPO (0.4 mmol, 62.5
mg), I2O5 (0.24 mmol, 80.1 mg), DBU (0.2 mmol, 30 ꢁL) and THF (2 mL) were
added. The reaction vessel was allowed to stir for 12 h at 80 °C. After the reaction, the
solution was concentrated in vacuum, only a trace amount of desired product 3aa was
detected and TEMPOꢀtrapped thiyl radical complex (pꢀMePhS–TEMPO) was also
detected by LCꢀMS experiment (see Supporting information).
(E)-(2-(phenylsulfonyl)vinyl)benzene (3aa). Compound 3aa was obtained in 87%
yield (44.9 mg) according to the general procedure. White solid; mp: 124.0ꢀ124.9oC.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.85 (d, J = 8.3 Hz, 2H), 7.68 (d, J = 15.5 Hz,
1H), 7.51ꢀ7.49 (m, 2H), 7.42ꢀ7.41 (m, 3H), 7.37 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 15.4
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Hz, 1H), 2.46 (s, 3H); C{1H}NMR (CDCl3, 125 MHz, ppm): δ 144.4, 141.9, 137.8,
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132.5, 131.1, 130.0, 129.1, 128.5, 127.7, 127.6, 21.6; HRMS calc. for C15H14O2SNa
(M+Na)+, 281.0612; found, 281.0616.
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(E)-(2-(phenylsulfonyl)vinyl)benzene (3ab). Compound 3ab was obtained in 91%
yield (44.4 mg) according to the general procedure. Yellow solid; mp: 71.7ꢀ73.0oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.96 (d, J = 7. 4 Hz, 2H), 7.70 (d, J = 15. 4 Hz, 1H),
7.64ꢀ7.61 (m, 1H), 7.55 (t, J = 7.3 Hz, 2H), 7.50ꢀ7.48 (m, 2H), 7.42ꢀ7.38 (m, 3H),
6.86 (d, J = 15. 4 Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 142.5, 140.7,
133.4, 132.4, 131.3, 129.4, 129.1, 128.6, 127.7, 127.3; HRMS calc. for C14H12O2SNa
(M+Na)+, 267.0456; found, 267.04569.
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(E)-1-methyl-3-(styrylsulfonyl)benzene (3ac). Compound 3ac was obtained in 73%
yield (37.6 mg) according to the general procedure. Yellow oil. 1H NMR (CDCl3, 500
MHz, ppm): δ 7.75ꢀ7.74 (m, 2H), 7.68 (d, J = 15.4 Hz, 1H), 7.50ꢀ7.48 (m, 2H), 7.44ꢀ
7.38 (m, 5H), 6.86 (d, J = 15.4Hz, 1H), 2.44 (s, 3H); 13C{1H}NMR (CDCl3, 125 MHz,
ppm): δ 142.3, 140.5, 139.7, 134.2, 132.4, 131.2, 129.2, 129.1, 128.6, 128.0, 127.4,
124.8, 21.4; HRMS calc. for C15H14O2SNa (M+Na)+, 281.0612; found, 281.0613.
(E)-1-methyl-2-(styrylsulfonyl)benzene (3ad). Compound 3ad was obtained in 56%
yield (28.9 mg) according to the general procedure. Yellow oil. 1H NMR (CDCl3, 500
MHz, ppm): δ 8.12ꢀ8.10 (m, 1H), 7.69 (d, J = 15.4 Hz, 1H), 7.52ꢀ7.48 (m, 3H), 7.42ꢀ
7.37 (m, 4H), 7.30 (d, J = 7.8 Hz, 1H), 6.85 (d, J = 15.3 Hz, 1H), 2.63 (s, 3H);
13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 142.9, 138.3, 138.1, 133.6, 132.6, 132.4,
131.2, 129.5, 129.1, 128.6, 126.7, 20.4; HRMS calc. for C15H14O2SNa (M+Na)+,
281.0612; found, 281.0615.
(E)-2,4-dimethyl-1-(styrylsulfonyl)benzene (3ae). Compound 3ae was obtained in
72% yield (39.1 mg) according to the general procedure. Yellow solid; mp: 74.6ꢀ
75.3oC. 1H NMR (CDCl3, 500 MHz, ppm): δ 7.99 (d, J = 8.1 Hz, 1H), 7.66 (d, J =
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15.4 Hz, 1H), 7.49ꢀ7.48 (m, 2H), 7.42ꢀ7.39 (m, 3H), 7.19 (d, J = 8.1 Hz, 1H), 7.10 (s,
1H), 6.83 (d, J = 15.4 Hz, 1H), 2.59 (s, 3H), 2.38 (s, 3H); 13C{1H}NMR (CDCl3, 125
MHz, ppm): δ 144.5, 142.3, 137.9, 135.4, 133.3, 132.5, 131.1, 129.7, 129.1, 128.5,
127.4, 127.1, 21.4, 20.3; HRMS calc. for C16H16O2SNa (M+Na)+, 295.0769; found,
295.0771.
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(E)-1,2-dimethoxy-4-(styrylsulfonyl)benzene (3af). Compound 3af was obtained in
94% yield (57.1 mg) according to the general procedure. Yellow solid; mp: 101.9ꢀ
103.0oC. 1H NMR (CDCl3, 500 MHz, ppm): δ 7.63 (d, J = 15.5 Hz, 1H), 7.58ꢀ7.56 (m,
1H), 7.49ꢀ7.47 (m, 2H), 7.42ꢀ7.38 (m, 4H), 6.98 (d, J = 8.5 Hz, 1H), 6.86 (d, J = 15.5
Hz, 1H), 3.95 (3H), 3.94 (3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 153.2, 149.3,
141.4, 132.5, 132.3, 131.1, 129.1, 128.5, 127.8, 121.9, 111.0, 109.8, 56.3, 56.3;
HRMS calc. for C16H16O4SNa (M+Na)+, 327.0667; found, 327.0669.
(E)-1-bromo-4-(styrylsulfonyl)benzene (3ag). Compound 3ag was obtained in 90%
yield (57.9 mg) according to the general procedure. White solid; mp: 101.2ꢀ102.6oC.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.81 (d, J = 8.7 Hz, 2H), 7.70ꢀ7.67 (m, 3H),
7.50ꢀ7.48 (m, 2H), 7.43ꢀ7.40 (m, 3H), 6.83 (d, J = 15.4 Hz, 1H); 13C{1H}NMR
(CDCl3, 125 MHz, ppm): δ 143.1, 139.8, 132.7, 132.2, 131.5, 129.2, 129.2, 128.7,
126.8; HRMS calc. for C14H11BrO2SNa (M+Na)+, 344.9561; found, 344.9563.
(E)-1-chloro-4-(styrylsulfonyl)benzene (3ah). Compound 3ah was obtained in 91%
yield (50.6 mg) according to the general procedure. White solid; mp: 83.4ꢀ84.5oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.89 (d, J = 8.7 Hz, 2H), 7.69 (d, J = 15.4 Hz, 1H),
7.52 (d, J = 8.6 Hz, 2H), 7.49 (d, J = 6.4 Hz, 2H), 7.43ꢀ7.38 (m, 3H), 6.83 (d, J = 15.4
Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 143.1, 140.1, 139.3, 132.2, 131.4,
129.7, 129.2, 129,2, 128.7, 126.9; HRMS calc. for C14H11O2ClSNa (M+Na)+,
301.0066; found, 301.0069.
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(E)-1-chloro-3-(styrylsulfonyl)benzene (3ai). Compound 3ai was obtained in 88%
yield (48.9 mg) according to the general procedure. White solid; mp: 71.1ꢀ72.7oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.94 (t, J = 1.8 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H),
7.71 (d, J = 15.4 Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.51ꢀ7.48 (m, 3H), 7.44ꢀ7.39 (m,
3H), 6.85 (d, J = 15.4 Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 143.5, 142.6,
135.6, 133.5, 132.1, 131.5, 130.7, 129.2, 128.7, 127.7, 126.6, 125.8; HRMS calc. for
C14H11O2ClSNa (M+Na)+, 301.0066; found, 301.0067.
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(E)-1-chloro-2-(styrylsulfonyl)benzene (3aj). Compound 3aj was obtained in 83%
yield (46.1 mg) according to the general procedure. White solid; mp: 93.3ꢀ94.0oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 8.23 (dd, J1 = 1.5 Hz, J2 = 8.0 Hz, 1H), 7.77 (d, J =
15.4 Hz, 1H), 7.57ꢀ7.51 (m, 4H), 7.49ꢀ7.46 (m, 1H), 7.44ꢀ7.39 (m, 3H), 7.08 (d, J =
15.4 Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 145.3, 138.3, 134.6, 132.8,
132.4, 131.9, 131.5, 130.7, 129.2, 128.7, 127.5, 125.3; HRMS calc. for
C14H11O2ClSNa (M+Na)+, 301.0066; found, 301.0065.
(E)-2,4-dichloro-1-(styrylsulfonyl)benzene (3ak). Compound 3ak was obtained in
87% yield (54.3 mg) according to the general procedure. White solid; mp: 80.8ꢀ
81.4oC. 1H NMR (CDCl3, 500 MHz, ppm): δ 8.16 (d, J = 8.6 Hz, 1H), 7.77 (d, J =
15.4 Hz, 1H), 7.53ꢀ7.51 (m, 3H), 7.46ꢀ7.40 (m, 4H), 7.03 (d, J = 15.4 Hz, 1H);
13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 145.8, 140.5, 136.9, 133.8, 132.2, 131.8,
131.7, 131.6, 129.2, 128.8, 127.8, 124.9; HRMS calc. for C14H10O2Cl2SNa (M+Na)+,
334.9676; found, 334.96768.
(E)-1-fluoro-4-(styrylsulfonyl)benzene (3al). Compound 3al was obtained in 86%
yield (45.1 mg) according to the general procedure. White solid; mp: 78.8ꢀ80.1oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.98ꢀ7.95 (m, 2H), 7.68 (d, J = 15.4 Hz, 1H), 7.50ꢀ
7.48 (m, 2H), 7.43ꢀ7.39 (m, 3H), 7.22 (d, J = 8.5 Hz, 1H), 6.84 (d, J = 15.4 Hz, 1H);
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13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 165.6 (d, J = 254.5 Hz), 142.7, 136.8 (d, J
=3.1 Hz), 132.2, 131.4, 130.5 (d, J = 254.5 Hz), 129.2, 128.6, 127.1, 116.8 (d, J =
22.5 Hz); HRMS calc. for C14H11FO2SNa (M+Na)+, 285.0361; found, 285.0363.
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(E)-1-(styrylsulfonyl)-2-(trifluoromethyl)benzene (3am). Compound 3am was
obtained in 84% yield (52.4 mg) according to the general procedure. Yellow solid; mp
79.7ꢀ81.2oC. 1H NMR (CDCl3, 500 MHz, ppm): δ 8.36 (d, J = 7.4 Hz, 1H), 7.90 (d, J
= 7.2 Hz, 1H), 7.79ꢀ7.76 (m, 2H), 7.70 (d, J = 15.4 Hz, 1H) 7.50ꢀ7.49 (m, 2H), 7.43ꢀ
7.38 (m, 3H), 6.99 (d, J = 15.4 Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ
144.4, 139.8 (d, J = 1.0 Hz), 133.5 132.8, 132.3 131.9, 131.5, 129.2, 129.0, 128.7,
128.4 (q, J = 6.2 Hz), 126.9 (q, J = 2.7 Hz), 122.7 (q, J = 272.3 Hz); HRMS calc. for
C15H11O2F3SNa (M+Na)+, 335.0330; found, 335.0331.
(E)-2-(styrylsulfonyl)naphthalene (3an). Compound 3an was obtained in 58% yield
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(34.1 mg) according to the general procedure. Yellow solid; mp: 129.9ꢀ131.2oC. H
NMR (CDCl3, 500 MHz, ppm): δ 8.55 (s, 1H), 8.00ꢀ7.97 (m, 2H), 7.92ꢀ7.88 (m, 2H),
7.75 (d, J = 15.4 Hz, 1H), 7.67ꢀ7.60 (m, 2H), 7.49 (d, J = 7.5 Hz, 2H), 7.41ꢀ7.37 (m,
3H), 6.92 (d, J = 15.4 Hz, 1H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): 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,
127.3, 122.6; HRMS calc. for C18H14O2SNa (M+Na)+, 317.0612; found, 317.0614.
(E)-4-(styrylsulfonyl)pyridine (3ao). Compound 3ao was obtained in 53% yield
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(25.9 mg) according to the general procedure. Yellow solid; mp: 83.1ꢀ84.0oC. H
NMR (CDCl3, 500 MHz, ppm): δ 8.88 (s, J = 6.0 Hz, 2H), 7.81ꢀ7.79 (m, 2H), 7.77 (d,
J = 15.4 Hz, 1H), 7.52ꢀ7.50 (m, 2H), 7.48ꢀ7.41 (m, 3H), 6.86 (d, J = 15.4 Hz, 1H);
13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 151.3, 149.0, 145.2, 131.9, 129.3, 128.9,
125.4, 120.6; HRMS calc. for C13H11NO2SNa (M+Na)+, 268.0408; found, 268.0409.
(E)-2-(styrylsulfonyl)pyridine (3ap). Compound 3ap was obtained in 36% yield
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(17.6 mg) according to the general procedure. Yellow solid; mp: 86.7ꢀ88.1oC. H
NMR (CDCl3, 500 MHz, ppm): δ 8.75 (d, J = 4.2 Hz, 1H), 8.15 (d, J = 7.9 Hz, 1H),
7.98ꢀ7.94 (dt, J1 = 1.7 Hz, J2 = 7.8 Hz, 1H), 7.79 (d, J = 15.5 Hz, 1H), 7.55ꢀ7.51 (m,
3H), 7.45ꢀ7.39 (m, 3H), 7.12 (d, J = 15.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz, ppm):
δ 158.6, 150.4, 145.2, 138.2, 132.4, 131.4, 129.1, 128.8, 127.1, 124.6, 121.9; HRMS
calc. for C13H11NO2SNa (M+Na)+, 268.0408; found, 268.0411.
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(E)-(2-(butylsulfonyl)vinyl)benzene (3aq). Compound 3aq was obtained in 43%
yield (19.2 mg) according to the general procedure. Yellow solid; mp: 83.1ꢀ84.0oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.60 (d, J = 15.5 Hz, 1H), 7.54ꢀ7.52 (m, 2H), 7.45ꢀ
7.43 (m, 3H), 6.83 (d, J = 15.5 Hz, 1H), 3.06 (t, J = 8.1 Hz, 2H), 1.85ꢀ1.78 (m, 2H),
1.50ꢀ1.45 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ
144.8, 132.3, 131.3, 129.2, 128.6, 124.7, 55.0, 24.6, 21.7, 13.6; HRMS calc. for
C12H16O2SNa (M+Na)+, 247.0769; found, 247.0771.
(E)-(2-(heptylsulfonyl)vinyl)benzene (3ar). Compound 3ar was obtained in 40%
yield (21.3 mg) according to the general procedure. Yellow oil. 1H NMR (CDCl3, 500
MHz, ppm): δ 7.60 (d, J = 15.5 Hz, 1H), 7.52 (d, J = 7.1 Hz, 2H), 7.43 (m, 3H), 6.83
(d, J = 15.5 Hz, 1H), 3.06 (t, J = 8.1 Hz, 2H), 1.86ꢀ1.79 (m, 2H), 1.45ꢀ1.40 (m, 2H),
1.34ꢀ1.26 (m, 6H), 0.87 (t, J = 5.9 Hz, 3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ
144.7, 132.3, 131.3, 129.2, 128.6, 124.8, 55.2, 31.4, 28.7, 28.4, 22.6, 22.5, 14.0;
HRMS calc. for C15H22O2SNa (M+Na)+, 289.1238; found, 289.1239.
(E)-1-methyl-4-(4-methylstyrylsulfonyl)benzene (3ba). Compound 3ba was
obtained in 79% yield (42.9 mg) according to the general procedure. Yellow solid; mp:
145.7ꢀ147.2oC. 1H NMR (CDCl3, 500 MHz, ppm): δ 7.84 (d, J = 8.3 Hz, 2H), 7.65 (d,
J = 15.4 Hz, 1H), 7.40ꢀ7.35 (m, 4H), 7.21 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 15.4 Hz,
1H), 2.45 (s, 3H), 2.39 (s, 3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 144.3,
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142.0, 141.7, 138.0, 129.9, 129.8, 129.7, 128.5, 127.7, 126.4, 21.6, 21.5; HRMS calc.
for C16H16O2SNa (M+Na)+, 295.0769; found, 295.0771.
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(E)-1-methyl-3-(2-tosylvinyl)benzene (3ca). Compound 3ca was obtained in 81%
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yield (44.0 mg) according to the general procedure. White solid; mp: 93.4ꢀ94.9oC. H
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NMR (CDCl3, 500 MHz, ppm): δ 7.85 (d, J = 8.3 Hz, 2H), 7.65 (d, J = 15.4 Hz, 1H ),
7.36 (d, J = 8.2 Hz, 2H), 7.31ꢀ7.29 (m, 3H), 7.25ꢀ7.23 (m, 1H), 6.85 (d, J = 15.4 Hz,
1H), 2.46 (s, 3H), 2.37 (s, 3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 144.3, 142.1,
138.8, 137.9, 132.4, 132.0, 130.0, 129.1, 129.0, 127.7, 127.4, 125.8, 21.6, 21.3;
HRMS calc. for C16H16O2SNa (M+Na)+, 295.0769; found, 295.0767.
(E)-1-fluoro-4-(2-tosylvinyl)benzene (3da). Compound 3da was obtained in 84%
yield (46.3 mg) according to the general procedure. Yellow solid; mp: 92.5ꢀ93.9oC.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.82 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 15.4 Hz,
1H), 7.49ꢀ7.45 (m, 2H), 7.35 (d, J = 8.3 Hz, 2H), 7.08 (t, J = 8.6 Hz, 2H), 6.78 (d, J =
15.4 Hz, 1H), 2.44 (s, 3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 164.3 (d, J =
251.3 Hz), 144.5, 140.6, 137.7, 130.6 (d, J = 8.7 Hz), 130.0, 128.7 (d, J = 8.7 Hz),
127.7, 127.4 (d, J = 2.4 Hz), 116.3 (d, J = 21.9 Hz), 21.6; HRMS calc. for
C15H13O2FSNa (M+Na)+, 299.0518; found, 299.0519.
(E)-1-chloro-4-(2-tosylvinyl)benzene (3ea). Compound 3ea was obtained in 80%
yield (46.7 mg) according to the general procedure. Yellow solid; mp: 143.7ꢀ144.8 oC.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.84 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 15.5 Hz,
1H), 7.43 (d, J = 8.6 Hz, 2H), 7.39ꢀ7.36 (m, 4H), 6.85 (d, J = 15.4 Hz, 1H), 2.46 (s,
3H); 13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 144.6, 140.4, 137.5, 137.1, 131.0,
130.0, 129.7, 129.4, 128.3, 127.8, 21.6; HRMS calc. for C15H13O2ClSNa (M+Na)+,
315.0222; found, 315.0225.
(E)-1-bromo-4-(2-tosylvinyl)benzene (3fa). Compound 3fa was obtained in 72%
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yield (48.4 mg) according to the general procedure. Yellow solid; mp: 153.8ꢀ155.4 oC.
1H NMR (CDCl3, 500 MHz, ppm): δ 7.85ꢀ7.84 (m, 2H), 7.61 (d, J = 15.4 Hz, 1H),
7.55ꢀ7.54 (m, 2H), 7.36 (t, J = 8.3 Hz, 4H), 6.86 (d, J = 15.4 Hz, 1H), 2.46 (s, 3H);
13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 144.6, 140.5, 137.5, 132.4, 131.4, 130.0,
129.9, 128.4, 127.8, 125.5, 21.7; HRMS calc. for C15H13BrO2SNa (M+Na)+, 358.9717;
found, 358.9719.
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(E)-1-nitro-3-(2-tosylvinyl)benzene (3ga). Compound 3ga was obtained in 48%
yield (29.1 mg) according to the general procedure. Yellow oil. 1H NMR (CDCl3, 500
MHz, ppm): δ 8.35 (t, J = 1.9 Hz, 1H), 8.29ꢀ8.26 (m, 1H), 7.87ꢀ7.86 (d, J = 8.4 Hz,
2H), 7.81 (d, J = 7.8Hz, 1H), 7.71 (d, J = 15.4 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H), 7.40
(d, J = 8.2 Hz, 2H), 7.03 (d, J = 15.5 Hz, 1H), 2.48 (s, 3H); 13C{1H}NMR (CDCl3,
125 MHz, ppm): δ 148.7, 145.0, 138.8, 136.9, 134.3, 134.2, 131.1, 130.2, 130,2, 128.0,
125.3, 122.7, 21.7; HRMS calc. for C15H13NO4SNa (M+Na)+, 326.0463; found,
326.0465.
(E)-2-(2-tosylvinyl)naphthalene (3ha). Compound 3ha was obtained in 78% yield
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(48.0 mg) according to the general procedure. Yellow solid; mp: 159.8ꢀ160.3oC. H
NMR (CDCl3, 500 MHz, ppm): δ 7.93 (s, 1H), 7.87ꢀ7.79 (m, 6H), 7.55ꢀ7.52 (m, 3H),
7.36 (d, J = 8.3 Hz, 2H), 6.95 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H); 13C{1H}NMR
(CDCl3, 125 MHz, ppm): δ 144.4, 142.0, 137.9, 134.5, 133.1, 130.9, 130.0, 129.9,
129.0, 128.7, 127.8, 127.8, 127.7, 127.0, 123.5, 21.6; HRMS calc. for C19H16O2SNa
(M+Na)+, 331.0769; found, 331.0773.
(E)-2-(2-tosylvinyl)pyridine (3ia). Compound 3ia was obtained in 82% yield (42.4
1
mg) according to the general procedure. Yellow solid; mp: 91.8ꢀ93.4oC. H NMR
(CDCl3, 500 MHz, ppm): δ 8.63 (d, J = 4.0 Hz, 1H), 7.86 (d, J = 8.4 Hz, 2H), 7.77ꢀ
7.73 (m, 1H), 7.64 (d, J = 14.9 Hz, 1H), 7.46 (d, J = 14.9 Hz, 1H), 7.42 (d, J = 7.8 Hz,
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1H), 7.36 (d, J = 8.0 Hz, 2H), 7.32ꢀ7.29 (m, 1H), 2.45 (m, 3H); 13C{1H}NMR (CDCl3,
125 MHz, ppm): δ 151.1, 150.3, 144.6, 140.0, 137.3, 137.0, 132.2, 130.0, 128.0, 125.4,
124.9, 21.6; HRMS calc. for C14H13NO2SNa (M+Na)+, 282.0565; found, 282.0567.
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(E)-1-methyl-4-(1-phenylprop-1-en-2-ylsulfonyl)benzene (3ja). Compound 3ja was
obtained in 44% yield (23.9 mg) according to the general procedure. Yellow solid; mp:
1
122.16ꢀ123.1oC. H NMR (CDCl3, 500 MHz, ppm): δ 7.83 (d, J = 8.2 Hz, 3H), 7.45ꢀ
7.36 (m, 7H), 2.46 (m, 3H), 2.13 (d, J = 1.4 Hz, 3H); 13C{1H}NMR (CDCl3, 125 MHz,
ppm): δ 144.3, 137.6, 137.0, 136.1, 133.9, 129.8, 129.6, 129.2, 128.7, 128.3, 21.6,
13.2; HRMS calc. for C16H16O2SNa (M+Na)+, 295.0769; found, 295.0771.
3-tosyl-1,2-dihydronaphthalene (3ka). Compound 3ka was obtained in 65% yield
(36.9 mg) according to the general procedure. Yellow solid; mp: 115.8ꢀ116.7oC. 1H
NMR (CDCl3, 500 MHz, ppm): δ 7.80 (d, J = 8.3 Hz, 2H), 7.56 (s, 1H), 7.32 (d, J =
8.1 Hz, 2H), 7.28ꢀ7.26 (m, 1H), 7.25ꢀ7.21 (m, 2H), 7.12 (d, J = 7.0 Hz, 1H), 2.86 (t, J
= 8.1 Hz, 2H), 2.51ꢀ2.47 (t, J = 8.1 Hz, 2H), 2.42 (s, 3H); 13C{1H}NMR (CDCl3, 125
MHz, ppm): δ 144.3, 138.5, 136.6, 135.6, 134.8, 131.1, 130.4, 129.9, 129.0, 128.0,
127.8, 127.2, 27.6, 21.7, 21.6; HRMS calc. for C17H16O2SNa (M+Na)+, 307.0769;
found, 307.0773.
(E)-1-(hex-1-enylsulfonyl)-4-methylbenzene (3la). Compound 3la was obtained in
23% yield (11.0 mg) according to the general procedure. Yellow oil; 1H NMR (CDCl3,
500 MHz, ppm): δ 7.75 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 6.99ꢀ6.93 (m,
1H), 6.31ꢀ6.28 (dt, J1 = 1.4 Hz, J2 = 15.1 Hz, 1H), 2.43 (s, 3H), 2.25ꢀ2.20 (m, 2H),
1.47ꢀ1.41 (m, 2H), 1.36ꢀ1.29 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H); 13C{1H}NMR (CDCl3,
125 MHz, ppm): δ 146.7, 144.2, 137.8, 130.6, 129.9, 127.6, 31.2, 29.7, 22.1, 21.6,
13.7; HRMS calc. for C13H18O2SNa (M+Na)+, 261.0925; found, 261.0929.
(E)-methyl 3-tosylacrylate (3ma). Compound 3ma was obtained in 40% yield (19.2
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mg) according to the general procedure. Yellow solid; mp: 106.1ꢀ107.4oC. 1H NMR
(CDCl3, 500 MHz, ppm): δ 7.80 (d, J = 8.3 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 7.33 (d,
J = 15.2 Hz, 1H), 6.80 (d, J = 15.2 Hz, 1H), 3.80 (s, 3H), 2.46 (s, 3H); 13C{1H}NMR
(CDCl3, 125 MHz, ppm): δ 164.0, 145.7, 143.7, 135.4, 130.3, 130.0, 128.4, 52.8, 21.7;
HRMS calc. for C11H12O4SNa (M+Na)+, 263.0354; found, 263.0357.
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(E)-methyl 3-tosylbut-2-enoate (3na). Compound 3na was obtained in 34% yield
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(17.2 mg) according to the general procedure. Yellow solid; mp: 55.2ꢀ56.6oC. H
NMR (CDCl3, 500 MHz, ppm): δ 7.82 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.0 Hz, 2H),
7.23ꢀ7.22 (q, J = 1. 5 Hz, 1H), 3.78 (s, 3H), 2.46 (s, 3H), 2.33 (d, J = 1. 5 Hz, 3H);
13C{1H}NMR (CDCl3, 125 MHz, ppm): δ 166.2, 145.2, 140.6, 137.7, 137.6, 130.1,
127.7, 53.0, 21.1, 13.3; HRMS calc. for C12H14O4SNa (M+Na)+, 277.0510; found,
277.0513.
ASSOCIATED CONTENT
AUTHOR INFORMATION
Corresponding Author
Eꢀmail: weiweiqfnu@163.com; huawang_qfnu@126.com.
Notes
The authors declare no competing financial interest.
ACKNOWLEGEMENTS
This work was supported by the National Natural Science Foundation of China (No.
21302109, 21302110, 21375075 and 21675099), the Taishan Scholar Foundation of
Shandong Province, the Natural Science Foundation of Shandong Province
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(ZR2015JL004 and ZR2016JL012), and International Cooperation Project of Qinghai
Province (2017ꢀHZꢀ806).
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Supporting Information
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Figures giving H and 13C{1H}NMR spectra for all compounds are prepared. This
information is available free of charge via the Internet at http://pubs.acs.org/.
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