Controllable Activation of β-Alkyl Nitroalkenes: Regioselective Synthesis of Allyl and Vinyl Sulfones

Article abstract of DOI:10.1021/acs.joc.0c02869

The regiospecific radical reactions of β-alkyl nitroalkenes with sulfonyl hydrazides depended to a great extent on the choice of a solvent and catalyst. In the presence of dimethylformamide (DMF), β-alkyl nitroalkenes more likely converted into electron-rich allyl nitro compounds, which reacted with sulfonyl hydrazides to afford allyl sulfones with high regioselectivity. While in acetonitrile (CH3CN), vinyl sulfones were obtained directly via sulfonation of electron-deficient β-alkyl nitroalkenes. The mechanism investigation revealed that the regioselectivity was controlled by the equilibrium of β-alkyl nitroalkenes and allyl nitro compounds.

Full text of DOI:10.1021/acs.joc.0c02869

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Article
Controllable Activation of β‑Alkyl Nitroalkenes: Regioselective
Synthesis of Allyl and Vinyl Sulfones
Ye Wang, Guowei Xiong, Chuanxin Zhang, and Yunfeng Chen*
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ABSTRACT: The regiospecific radical reactions of β-alkyl nitro-
alkenes with sulfonyl hydrazides depended to a great extent on the
choice of a solvent and catalyst. In the presence of dimethylformamide
(DMF), β-alkyl nitroalkenes more likely converted into electron-rich
allyl nitro compounds, which reacted with sulfonyl hydrazides to
afford allyl sulfones with high regioselectivity. While in acetonitrile
(CH3CN), vinyl sulfones were obtained directly via sulfonation of
electron-deficient β-alkyl nitroalkenes. The mechanism investigation revealed that the regioselectivity was controlled by the
equilibrium of β-alkyl nitroalkenes and allyl nitro compounds.
general, these reactions require precise condition control,
prefunctionalization of allyl compounds or expensive cata-
lysts.12 For the synthesis of vinyl sulfones, some methods have
also been established, such as sulfide oxidation,13 β-elimination
seleno(halogenated) sulfones,14 and direct cross coupling of
sulfonyl derivatives with olefins15 or alkynes.16 In spite of these
achievements, achieving regiospecific control in the synthesis
of allyl sulfones and vinyl sulfones is challenging and
rewarding.
Previously, we have developed a metal-free direct allyl
sulfonation of β-alkyl nitroalkenes with sodium sulfites as a
sulfonyl precursor, it was found that sodium sulfites or DMF/
DMSO solvents could be served as a Lewis base17 to promote
the isomerization of β-alkyl nitroalkenes to allyl nitro
compounds, and the sulfonyl radical tended to react with the
electron-rich allyl nitro equilibrium isomers; in this case, vinyl
sulfones could not be formed (Scheme 2A).18 In continuation
of the development of new reactivities of β-alkyl nitroalkenes,
herein, we disclose an oxidative radical reaction of β-alkyl
nitroalkenes and sulfonyl hydrazides. By tuning the sulfonyl
radical source and choice of different solvents and catalysts, the
reactions could form allyl sulfones and vinyl sulfones via a new
equilibrium-control strategy of β-alkyl nitroalkenes and allyl
nitro compounds (Scheme 2B).
INTRODUCTION
■
The main challenge in free-radical reactions is the methods for
activating specific reaction sites for organic substrates or
control different reactive sites in a molecule.1 The strategies for
high selectivity are mainly reflected in the selection of a
catalyst,2 oxidant,3 ligand,4 solvent,5 or acid/base.6 Regiose-
lective synthesis of different isomeric products from the same
reactants is of great significance for method development. Allyl
and vinyl sulfones are regioisomers; they are both important
structural motifs, which widely exist in bioactive compounds.7
Furthermore, they play important roles in the field of synthetic
organic chemistry due to the general molecular framework of
various organic transformations.8 Thus, increasing attentions
have been devoted to the preparation of allyl sulfones and vinyl
sulfones (Scheme 1).9 The directly method of preparing allyl
sulfones is to oxidize the corresponding sulfides with
stoichiometric strong oxidants.10 Another approach is Pd or
Ir-catalyzed allyl substitution (Tsuji−Trost reaction).11 In
Scheme 1. Synthesis of Allyl and Vinyl Sulfones
Received: December 2, 2020
Published: February 15, 2021
https://dx.doi.org/10.1021/acs.joc.0c02869
© 2021 American Chemical Society
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other catalysts were tested (for detailed results see the
Supporting Information). It was found that FeCl3 was the
most effective catalyst to obtain 3a (entries 4−6). Gratefully, a
higher yield was obtained when DMF was used as a solvent
(entry 7). Different types of oxidants including DTBP, H2O2,
and K2S2O8 were also screened (entries 8−10), and it turned
out that DTBP exhibited the best result, the yield of 3a was up
to 92%, and 4a was totally inhibited (entry 8). Moreover,
reducing the temperature is unfavorable to the reaction (entry
11).
Scheme 2. Activation of β-Alkyl Nitroalkenes
Exceptionally, under the I2/TBHP system, when DMF was
replaced by CH3CN, 4a was obtained as the major product
(entry 12). Then, other conditions were also tested, the results
showed that, no matter what catalytic system was chosen
(FeCl3/DTBP, FeCl3/TBHP, TBAI/TBHP, entries 13−15),
4a was the major product as long as CH3CN served as the
solvent (for more solvent studies see the Supporting
Information); under the TBAI/TBHP system, the formation
of 3a was inhibited totally, and 4a was obtained with 94%
yield. Replacing different oxidants, such as K2S2O8 and H2O2,
resulted in a slight decrease in the yield of 4a (entries 16−17).
It was noteworthy that the addition of DMF or other base was
in favor of the formation of 3a and reduced the yield of 4a
(entries 18−20), which implied that DMF or other bases were
probably served as a Lewis base to promote the formation of
allyl sulfones.17,18
With the optimal condition in hand, we start to investigate
the scope of the reactions. For the synthesis of allyl sulfones,
the results are summarized in Table 2. The reactions of β-alkyl
nitroalkenes containing electron-donating or electron-with-
drawing groups with sulfonyl hydrazides proceeded efficiently
and provided the corresponding products in moderate-to-good
yields. Meanwhile, it was found that yields of sulfonyl
hydrazides with electron-donating groups (R = CH3, OMe)
were higher than that with electron-withdrawing groups (R =
F, Cl, Br, NO2), but reactions of p-nitrobenzenesulfonyl
hydrazides with β-alkyl nitroalkenes resulted in lower yields.
The scope of vinyl sulfones was also investigated (Table 3).
Different β-alkyl nitroalkenes and sulfonyl hydrazides were also
suitable substrates, which all afforded E-products with good-to-
excellent yields, and β-ethyl nitroalkene also provided good
yields (4m and 4o). The same substituent effect was also
observed, it showed that the sulfonyl hydrazides with electron-
donating groups gave higher yields, and the substituent effects
were not obvious for β-alkyl nitroalkenes.
To gain insights into the reaction mechanism, 1a and 2a
reacted in the presence of 2,2,6,6-tetramethylpiperidinooxy
(TEMPO, 3 equiv). However, 3a or 4a was not detected,
which implied that the reaction could involve a radical process.
During the formation of 3a (under condition A), we detected
the isomeric 1a′ intermediate; further investigation showed
that 3a was obtained with 94% isolated yield in only 1.5 h
under condition A for the reaction of 1a′ and 2a, which
revealed that allyl sulfones could be formed from isomeric allyl
nitro compounds (Scheme 3A).
To explore the isomerization of β-alkyl nitroalkenes,
following experiments were carried out (Scheme 3B). The
results showed that 1a did not convert to 1a′ at DMF in 30 °C
or at CH3CN in 80 °C with 2a. However, 1a gradually
converted to 1a′ at DMF in 100 °C and remained an
equilibrium at 50% conversion, which demonstrated that DMF
could be served as a Lewis base17 to effectively promote the
isomerization of 1a at 100 °C; a proposed mechanism is
RESULTS AND DISCUSSION
■
We initiated our research on the model reaction of (E)-(1-
nitroprop-1-en-2-yl)benzene (1a) with 4-methylbenzenesulfo-
nohydrazide (2a) under different reaction conditions (Table
1). When the reaction ran in DMSO at 100 °C, the allyl
sulfone 3a was obtained as only product in 45% yield (entry
1). If the reaction performed using an I2/TBHP catalytic
system, 3a was obtained in 61% yield; however, the vinyl
sulfone 4a was also formed (entry 2). In addition, the TBAI/
TBHP reaction system gave a similar result (entry 3). Then,
a
Table 1. Optimization of Reaction Conditions
3a/4a/conv.
b
entry
catalyst
oxidant
additive
solvent
(%)
c
1
2
3
4
5
6
7
8
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
45/0/100
61/5/100
65/7/100
54/6/100
63/12/100
68/9/100
87/3/100
92/0/100
61/5/100
19/9/100
47/0/80
9/72/100
13/80/100
12/75/100
0/94/100
8/81/100
10/78/100
54/27/100
62/30/100
0/84/100
e
c
I2
TBAI
TBHP
f
c
TBHP
TBHP
TBHP
TBHP
TBHP
c
FeCl2
Fe(NO3)3
FeCl3
FeCl3
FeCl3
FeCl3
FeCl3
FeCl3
I2
FeCl3
FeCl3
TBAI
TBAI
TBAI
TBAI
TBAI
TBAI
c
c
c
DMF
g
c
DTBP
DMF
c
9
K2S2O8
H2O2
DMF
c
10
11
12
13
14
15
16
17
18
19
20
DMF
d
DTBP
TBHP
TBHP
DTBP
TBHP
K2S2O8
H2O2
TBHP
TBHP
TBHP
DMF
d
d
c
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
d
d
d
d
d
d
DMF
NaOAc
Et3N
a
Reaction conditions: 1a (0.5 mmol), 2a (1 mmol), catalyst (0.1
b
mmol), oxidant (1 mmol), additive (2 mmol), open air. Isolated
c
d
yield. Reacted in 100 °C (oil bath), 2 h. Reacted in 80 °C (oil
e
f
bath), 2 h. TBHP: 2-hydroperoxy-2-methylpropane. TBAI:
g
tetrabutylammonium iodide. DTBP: 2-(tert-butylperoxy)-2-methyl-
propane.
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a
a
Table 2. Scope of Allyl Sulfones
Table 3. Scope of Vinyl Sulfones
a
General conditions: β-alkyl nitroalkenes (0.5 mmol), sulfonyl
hydrazides (1 mmol), TBAI (0.1 mmol), and TBHP (1 mmol) in 3
mL of CH3CN, in 80 °C (oil bath) for 2 h; isolated yield based on β-
alkyl nitroalkenes.
a
General conditions: β-alkyl nitroalkenes (0.5 mmol), sulfonyl
hydrazides (1 mmol), FeCl3 (0.1 mmol), and DTBP (1 mmol) in 3
mL of DMF, in 100 °C (oil bath) for 2 h; isolated yield based on β-
alkyl nitroalkenes.
Based on these results, a possible mechanism is proposed in
Scheme 5. In the TBAI/TBHP or FeCl3/DTBP reaction
system, sulfonyl hydrazine converted to a sulfonyl radical.
Under the condition A, 1a was isomerized to an allyl nitro
compound (1a′), which reacted with sulfonyl radical easily to
afford allyl sulfone (3a). Under the condition B, the sulfonyl
radical preferentially reacted with 1a directly to obtain alkenyl
sulfone (4a). The key for the selectivity is not the formation of
the sulfonyl radical but the equilibrium of β-alkyl nitroalkene
and allyl nitro compound.
outlined in Scheme 3C. Meanwhile, 1a′ could not be obtained
from 1a under the condition of FeCl3/DTBP and CH3CN as
solvents at 80 °C. It is noteworthy that 1a could be converted
to 1a′ in a small amount under the TBAI/TBHP condition
with CH3CN as the solvent in 80 °C.
To disclose the reaction process of 1a and 2a under the
condition A or B, the content of each component was
monitored (Scheme 3D). Under the condition A, 1a was
consumed rapidly; with the formation of 3a, 1a′ was formed
instantly. Overall, the 1a and 1a′ should be all converted to
product 3a. Under the condition B, the conversion of 1a to 1a′
is not likely to be the dominant one, so 2a reacted with 1a
directly to obtain 4a. Notably, the precursor S-(p-tolyl) 4-
methylbenzenesulfonothioate 2a′ of the sulfonylhydrazine
radical could be obtained under FeCl3/DTBP to participate
in the reaction. Under condition B, the reaction of 1a′ and 2a′
still gave 3a, which revealed the reaction selectivity was not
controlled by the sulfonyl radical source (Scheme 3E).
In addition, the conversion between 3a and 4a was
systematically attempted (Scheme 4). It found that 4a did
not converted to 3a under the condition A, and 3a could yield
4a in only 12% yield under the condition B, which
demonstrated that 4a is not likely formed from the
isomerization of 3a.
CONCLUSIONS
■
In conclusion, we have developed an oxidative radical reaction
of β-alkyl nitroalkenes and sulfonyl hydrazides. The reaction
proceeded under mild conditions and showed a wide substrate
scope. By tuning the solvent and catalytic system, the vinyl and
allyl sulfones could be selective obtained in good-to-excellent
yields. This work sheds some lights on the study of the diverse
reactivity of β-alkyl nitroalkenes.
EXPERIMENTAL SECTION
■
General Information. Unless otherwise stated, all chemicals used
in the experiments were obtained from commercial sources and used
directly without further treatment. TLC was performed with the
detection of compounds with UV light. Flash column chromatography
purification of the products was accomplished on silica gel (200−300
mesh). Petroleum ether (PE) (60−90 °C) and ethyl acetate (EA)
were used as eluents for silica gel chromatography. Melting points for
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Scheme 3. Control Experiments
Scheme 4. Interconversion of 3a and 4a
Scheme 5. Plausible Mechanism
finished (as monitored by TLC), the mixture was quenched with
water and extracted with EtOAc (3 × 25 mL). The combined organic
layers were dried over anhydrous Na2SO4, and the solvent was
evaporated in vacuo. The resulting mixture was chromatographed on
silica gel by eluting with petroleum ether/ethyl acetate to provide the
product.
General Procedures for the Synthesis of 3a in the Gram
Scale. A mixture of (E)-(1-nitroprop-1-en-2-yl)benzene (1a) (5
mmol), 4-methylbenzenesulfonohydrazide (2a) (10 mmol), FeCl3 (1
mmol), and DTBP (10 mmol) in 12 mL of DMF was stirred under an
air atmosphere in a 25 mL tube at 100 °C (oil bath). After the
reaction finished (as monitored by TLC), the mixture was quenched
with water and extracted with EtOAc (3 × 25 mL). The combined
organic layers were dried over anhydrous Na2SO4, and the solvent was
evaporated in vacuo. The resulting mixture was chromatographed on
silica gel by eluting with petroleum ether/ethyl acetate to provide the
product 3a (1.12 g, 82%).
General Procedure for the Synthesis of Vinyl Sulfones. A
mixture of (E)-(1-nitroprop-1-en-2-yl)benzene (1a) (0.5 mmol), 4-
methylbenzenesulfonohydrazide (2a) (1 mmol), TBAI (0.1 mmol),
and TBHP (1 mmol) in 3 mL of CH3CN was stirred under an air
atmosphere in a 10 mL tube at 80 °C (oil bath). After the reaction
finished (as monitored by TLC), the mixture was quenched with
water and extracted with EtOAc (3 × 25 mL). The combined organic
layers were dried over anhydrous Na2SO4, and the solvent was
evaporated in vacuo. The resulting mixture was chromatographed on
silica gel by eluting with petroleum ether/ethyl acetate to provide the
product.
all solid products were measured on an X − 4A melting point
apparatus without correction. 1H and 13C NMR spectra were
recorded at 22 °C on Bruker AV 400 MHz spectrometers with
tetramethylsilane (TMS) as an internal standard. 1H and 13C chemical
shifts in NMR spectra were referenced relative to signals of CDCl3 (δ
7.26 ppm for 1H and 77.0 ppm for 13C). High-resolution mass spectra
(HRMS) were acquired on Waters Acquity UPLC Class I/Xevo
G2Q−TOF.
General Procedure for the Synthesis of Allyl Sulfones. A
mixture of (E)-(1-nitroprop-1-en-2-yl)benzene (1a) (0.5 mmol), 4-
methylbenzenesulfonohydrazide (2a) (1 mmol), FeCl3 (0.1 mmol),
and DTBP (1 mmol) in 3 mL of DMF was stirred under an air
atmosphere in a 10 mL tube at 100 °C (oil bath). After the reaction
General Procedures for the Synthesis of 4a in the Gram
Scale. A mixture of (E)-(1-nitroprop-1-en-2-yl)benzene (1a) (5
mmol), 4-methylbenzenesulfonohydrazide (2a) (10 mmol), TBAI (1
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mmol), and TBHP (10 mmol) in 12 mL of CH3CN was stirred under
an air atmosphere in a 25 mL tube at 80 °C (oil bath). After the
reaction finished (as monitored by TLC), the mixture was quenched
with water and extracted with EtOAc (3 × 25 mL). The combined
organic layers were dried over anhydrous Na2SO4, and the solvent was
evaporated in vacuo. The resulting mixture was chromatographed on
silica gel by eluting with petroleum ether/ethyl acetate to provide the
product 4a (1.13 g, 83%).
= 7.88, 2.08 Hz, 2H), 6.68 (m, 1H), 5.60 (s, 1H), 5.26 (s, 1H), 4.25
(s, 2H), 3.76 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ
159.5, 139.9, 137.3, 136.3, 132.1, 130.2, 129.5, 129.1, 122.4, 118.7,
113.1, 112.5, 62.3, 55.3. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H15BrO3SNa 388.9817; found 388.9806.
1-Nitro-3-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (3h). White
solid (121.2 mg, 80%); mp 105−106 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.10); H NMR (400
MHz, CDCl3, ppm) δ 8.13−8.02 (m, 2H), 7.79 (d, J = 7.60 Hz, 2H),
7.68 (d, J = 7.64 Hz, 1H), 7.57 (t, J = 7.40 Hz, 1H), 7.46 (t, J = 7.60
Hz, 3H), 5.72 (s, 1H), 5.38 (s, 1H), 4.29 (s, 2H). 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 148.1, 140.4, 138.0, 134.6, 133.9, 132.2,
129.5, 129.1, 128.5, 124.5, 122.8, 121.1, 61.7. HRMS (ESI-TOF) m/
z: [M + H]+ calcd for C15H13NO4SH 304.0638; found 304.0638.
1-Nitro-3-(3-tosylprop-1-en-2-yl)benzene (3i). White solid (133.2
mg, 84%); mp 143−145 °C; purification by silica gel chromatography
Characterization Data. S-(p-Tolyl) 4-Methylbenzenesulfono-
thioate (2a′).19 White solid (125.1 mg, 90%); mp 76−78 °C;
purification by silica gel chromatography (eluent: PE/EA = 20:1, Rf =
0.21); 1H NMR (400 MHz, CDCl3, ppm) δ 7.45 (d, J = 8.3 Hz, 2H),
7.25−7.19 (m, 4H), 7.13 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H), 2.37 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 144.6, 142.0, 140.3,
136.4, 130.1, 129.3, 127.5, 124.5, 21.6, 21.4. HRMS (ESI-TOF) m/z:
[M + Na]+ calcd for C14H14O2S2Na 301.0327; found 301.0315.
1-Methyl-4-((2-phenylallyl)sulfonyl)benzene (3a).9c White solid
(125.1 mg, 92%); mp 97−98 °C; purification by silica gel
1
(eluent: PE/EA = 15:1, Rf = 0.11); H NMR (400 MHz, CDCl3,
ppm) δ 8.09−7.94 (m, 2H), 7.66 (dd, J = 0.72, 6.68 Hz, 3H), 7.44 (t,
J = 8.04 Hz, 1H), 7.21 (d, J = 7.96 Hz, 2H), 5.69 (s, 1H), 5.35 (s,
1H), 4.27 (s, 2H), 2.35 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3,
ppm) δ 148.0, 145.0, 140.4, 134.9, 134.7, 132.3, 129.6, 129.4, 128.4,
124.3, 122.5, 121.0, 61.7, 21.4. HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C16H15NO4SNa 340.0614; found 340.0601.
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.13); H NMR (400
MHz, CDCl3, ppm) δ 7.64 (d, J = 5.32 Hz, 2H), 7.28−7.17 (m, 7H),
5.56 (s, 1H), 5.19 (s, 1H), 4.23 (s, 2H), 2.36 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 144.5, 138.7, 136.4, 135.3, 129.4, 128.5,
128.2, 127.8, 126.1, 121.6, 62.0, 21.4.
((2-Phenylallyl)sulfonyl)benzene (3b).9c White solid (117.4 mg,
91%); mp 45−47 °C; purification by silica gel chromatography
1-Nitro-3-(3-((4-nitrophenyl)sulfonyl)prop-1-en-2-yl)benzene
(3j). White solid (130.5 mg, 75%); mp 115−117 °C; purification by
1
1
silica gel chromatography (eluent: PE/EA = 15:1, Rf = 0.12); H
(eluent: PE/EA = 15:1, Rf = 0.11); H NMR (400 MHz, CDCl3,
NMR (400 MHz, CDCl3, ppm) δ 8.35 (d, J = 7.84 Hz, 2H), 8.15 (d, J
= 8.92 Hz, 2H), 8.04 (d, J = 7.68 Hz, 2H), 7.72 (d, J = 7.96 Hz, 1H),
7.52 (t, J = 7.96 Hz, 1H), 5.79 (s, 1H), 5.38 (s, 1H), 4.36 (s, 2H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 150.9, 143.6, 139.9, 134.0,
132.2, 130.1, 129.8, 125.2, 124.3, 123.2, 121.1, 61.7. HRMS (ESI-
TOF) m/z: [M + Na]+ calcd for C15H12N2O6SNa 371.0308; found
371.0295.
ppm) δ 7.77 (d, J = 5.20 Hz, 2H), 7.52 (t, J = 4.92 Hz, 1H), 7.40 (t, J
= 5.12 Hz, 2H), 7.27−7.20 (m, 5H), 5.57 (s, 1H), 5.20 (s, 1H), 4.26
(s, 2H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 138.6, 138.3,
136.3, 133.5, 128.8, 128.5, 128.3, 127.9, 126.1, 121.7, 61.9.
1-Fluoro-4-((2-phenylallyl)sulfonyl)benzene (3c).18 White solid
(115.9 mg, 84%); mp 84−86 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.12); H NMR (400
MHz, CDCl3, ppm) δ 7.76 (dd, J = 5.68, 3.44 Hz, 2H), 7.23 (m, 5H),
7.07 (t, J = 5.64 Hz, 2H), 5.60 (s, 1H), 5.24 (s, 1H), 4.28 (s, 2H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 165.7 (d, J = 256.3 Hz),
138.5, 136.5, 134.3 (d, J = 2.9 Hz), 131.5 (d, J = 9.6 Hz), 128.4,
128.1, 126.1, 122.0, 116.1 (d, J = 22.7 Hz), 62.2.
1-Fluoro-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3k).18
White solid (127.0 mg, 83%); mp 131−132 °C; purification by silica
1
gel chromatography (eluent: PE/EA = 15:1, Rf = 0.11); H NMR
(400 MHz, CDCl3, ppm) δ 7.81−7.72 (m, 2H), 7.18 (dt, J = 2.08,
4.64 Hz, 2H), 7.13−7.04 (m, 2H), 6.77 (dt, J = 2.12, 4.64 Hz, 2H),
5.61 (s, 1H), 5.32 (s, 1H), 4.22 (s, 2H), 3.87 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3, ppm) δ 165.7 (d, J = 256.2 Hz), 159.6, 135.9,
134.5, 131.5 (d, J = 9.6 Hz), 130.9, 127.4, 120.1, 116.0 (d, J = 22.7
Hz), 113.8, 62.4, 55.3.
1-Nitro-3-((2-phenylallyl)sulfonyl)benzene (3d). White solid
(122.7 mg, 81%); mp 110−111 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.14); H NMR (400
MHz, CDCl3, ppm) δ 8.48 (s, 1H), 8.31 (d, J = 8.16 Hz, 1H), 8.05 (d,
J = 7.72 Hz, 1H), 7.59 (t, J = 7.96 Hz, 1H), 7.16 (s, 5H), 5.63 (s, 1H),
5.35 (s, 1H), 4.37 (s, 2H). 13C{1H} NMR (100 MHz, CDCl3, ppm)
147.8, 140.3, 137.9, 136.0, 134.0, 128.5, 128.3, 128.0, 126.1, 124.2,
122.8, 62.1. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C15H13NO4SNa 326.0457; found 326.0443.
1-Chloro-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3l).18
White solid (140.1 mg, 87%); mp 120−121 °C; purification by silica
1
gel chromatography (eluent: PE/EA = 15:1, Rf = 0.14); H NMR
(400 MHz, CDCl3, ppm) δ 7.67 (d, J = 8.56 Hz, 2H), 7.37 (d, J =
8.52 Hz, 2H), 7.16 (dt, J = 1.92, 4.84 Hz, 2H), 6.76 (dt, J = 1.92, 4.88
Hz, 2H), 5.50 (s, 1H), 5.11 (s, 1H), 4.24 (s, 2H), 3.78 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 159.6, 140.2, 136.9, 135.8,
130.8, 130.1, 129.0, 127.4, 120.2, 113.8, 62.4, 55.3.
1-Methoxy-3-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (3e).
White solid (128.2 mg, 89%); mp 78−80 °C; purification by silica
1
gel chromatography (eluent: PE/EA = 12:1, Rf = 0.13); H NMR
1-Bromo-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3m).18
Yellow oil (155.6 mg, 85%); purification by silica gel chromatography
(400 MHz, CDCl3, ppm) δ 7.81−7.73 (m, 2H), 7.50 (t, J = 7.32 Hz,
1H), 7.40 (t, J = 7.96 Hz, 2H), 7.12 (t, J = 7.96 Hz, 1H), 6.83 (dt, J =
7.76, 0.68 Hz, 1H), 6.80−6.69 (m, 2H), 5.57 (s, 1H), 5.20 (s, 1H),
4.25 (s, 2H), 3.72 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ
159.2, 140.0, 138.1, 136.1, 133.5, 129.2, 128.7, 128.4, 121.8, 118.5,
113.2, 111.9, 61.8, 55.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H16O3SNa 311.0712; found 311.0698.
1
(eluent: PE/EA = 15:1, Rf = 0.11); H NMR (400 MHz, CDCl3,
ppm) δ 7.71 (d, J = 8.88 Hz, 2H), 7.30−7.26 (m, 2H), 7.00−6.89 (m,
4H), 5.55 (s, 1H), 5.20 (s, 1H), 4.24 (s, 2H), 3.87 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3, ppm) δ 163.8, 137.7, 135.9, 131.5, 130.8,
129.7, 127.9, 122.2, 122.1, 114.1, 62.3, 55.7.
1-Methoxy-3-(3-tosylprop-1-en-2-yl)benzene (3f).9g White solid
(137.5 mg, 91%); mp 89−90 °C; purification by silica gel
1-Methoxy-4-((2-(p-tolyl)allyl)sulfonyl)benzene (3n). White solid
(137.5 mg, 91%); mp 93−94 °C; purification by silica gel
1
1
chromatography (eluent: PE/EA = 12:1, Rf = 0.10); H NMR (400
chromatography (eluent: PE/EA = 12:1, Rf = 0.11); H NMR (400
MHz, CDCl3, ppm), δ 7.68 (d, J = 8.72 Hz, 2H), 7.17 (d, J = 8.00 Hz,
2H), 7.05 (d, J = 7.88 Hz, 2H), 6.87 (d, J = 8.72 Hz, 2H), 5.54 (s,
1H), 5.12 (s, 1H), 4.23 (s, 2H), 3.83 (s, 3H), 2.30 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3, ppm) δ 163.5, 137.7, 136.5, 135.8, 130.7,
129.8, 129.0, 126.0, 120.7, 113.9, 62.2, 55.5, 21.0. HRMS (ESI-TOF)
m/z: [M + Na]+ calcd for C17H18O3SNa 325.0869; found 325.0855.
1-Fluoro-4-((2-(p-tolyl)allyl)sulfonyl)benzene (3o).18 White solid
(116.1 mg, 80%); mp 83−84 °C; purification by silica gel
MHz, CDCl3, ppm) δ 7.65 (d, J = 8.24 Hz, 2H), 7.24−7.10 (m, 3H),
6.89−6.80 (m, 1H), 6.80−6.70 (m, 2H), 5.57 (s, 1H), 5.21 (s, 1H),
4.23 (s, 2H), 3.75 (s, 3H), 2.37 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 159.3, 144.5, 140.2, 136.4, 135.2, 129.4, 129.2, 128.5,
121.8, 118.6, 113.2, 112.0, 62.1, 55.1, 21.4.
1-(3-((4-Bromophenyl)sulfonyl)prop-1-en-2-yl)-3-methoxyben-
zene (3g). White solid (159.2 mg, 87%); mp 138−140 °C;
purification by silica gel chromatography (eluent: PE/EA = 12:1, Rf
1
1
= 0.12); H NMR (400 MHz, CDCl3, ppm) δ 7.59 (d, J = 8.56 Hz,
chromatography (eluent: PE/EA = 15:1, Rf = 0.13); H NMR (400
2H), 7.52 (d, J = 8.60 Hz, 2H), 7.15 (t, J = 7.96 Hz, 1H), 6.78 (dd, J
MHz, CDCl3, ppm) δ 7.80−7.73 (m, 2H), 7.15−7.01 (m, 6H), 5.56
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J. Org. Chem. 2021, 86, 4018−4026

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
(s, 1H), 5.16 (s, 1H), 4.26 (s, 2H), 2.31 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 165.72 (d, J = 256.2 Hz), 138.1, 136.3, 135.6,
134.4 (d, J = 3.2 Hz), 131.52 (d, J = 9.6 Hz), 129.1, 126.0, 121.0,
116.0 (d, J = 22.7 Hz), 62.3, 21.0.
(100 MHz, CDCl3, ppm) δ 141.0, 140.2, 137.2, 137.1, 135.9, 132.1,
130.2, 129.0, 128.8, 127.5, 127.1, 127.0, 126.6, 122.0, 62.1. HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C21H17BrO2SNa 435.0025;
found 435.0008.
2-(3-Tosylprop-1-en-2-yl)naphthalene (3x).9c White solid (145.0
mg, 90%); mp 114−116 °C; purification by silica gel chromatography
1-Methyl-4-(3-((4-nitrophenyl)sulfonyl)prop-1-en-2-yl)benzene
(3p). White solid (123.7 mg, 78%); mp 113−114 °C; purification by
1
1
silica gel chromatography (eluent: PE/EA = 15:1, Rf = 0.12); H
(eluent: PE/EA = 15:1, Rf = 0.12); H NMR (400 MHz, CDCl3,
NMR (400 MHz, CDCl3, ppm) δ 8.19 (dt, J = 1.96, 8.88 Hz, 2H),
7.90 (dt, J = 2.24, 8.92 Hz, 2H), 7.13−6.94 (m, 4H), 5.58 (s, 1H),
5.22 (s, 1H), 4.33 (s, 2H), 2.28 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 150.5, 143.8, 138.5, 135.8, 135.0, 130.2, 129.2, 126.0,
123.8, 121.8, 62.3, 21.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H15NO4SNa 340.0614; found 340.0601.
ppm) δ 7.80−7.74 (m, 1H), 7.73−7.67 (m, 2H), 7.64 (d, J = 8.20 Hz,
2H), 7.57 (d, J = 0.84 Hz, 1H), 7.50−7.37 (m, 3H), 7.09 (d, J = 8.04
Hz, 2H), 5.73 (s, 1H), 5.34 (s, 1H), 4.37 (s, 2H), 2.21 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 144.6, 136.5, 135.8, 135.3,
132.9, 132.7, 129.4, 128.6, 128.1, 127.9, 127.4, 126.2, 126.2, 125.4,
124.0, 122.0, 62.2, 21.3.
1-Bromo-4-(3-((4-chlorophenyl)sulfonyl)prop-1-en-2-yl)benzene
(E)-1-Methyl-4-((2-phenylprop-1-en-1-yl)sulfonyl)benzene
(3q).18 Yellow oil (153.5 mg, 83%); purification by silica gel
(4a).9b White solid (127.9 mg, 94%); mp 90−91 °C; purification by
1
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.15); H NMR (400
silica gel chromatography (eluent: PE/EA = 20:1, Rf = 0.12); H
MHz, CDCl3, ppm) δ 7.69 (d, J = 5.72 Hz, 2H), 7.41 (dd, J = 5.76,
6.96 Hz, 4H), 7.14 (d, J = 5.68 Hz, 2H), 5.60 (s, 1H), 5.22 (s, 1H),
4.23 (s, 2H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 140.7, 137.4,
136.6, 135.4, 131.6, 130.1, 129.3, 127.8, 122.6, 122.4, 62.1.
NMR (400 MHz, CDCl3, ppm) δ 7.85 (d, J = 8.32 Hz, 2H), 7.47−
7.30 (m, 7H), 6.59 (d, J = 1.24 Hz, 1H), 2.52 (d, J = 1.20 Hz, 3H),
2.44 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 152.9, 144.1,
140.2, 139.3, 129.8, 129.8, 128.7, 127.8, 127.3, 126.3, 21.6, 17.2.
(E)-((2-Phenylprop-1-en-1-yl)sulfonyl)benzene (4b).9i Colorless
oil (118.7 mg, 92%); purification by silica gel chromatography
1-Fluoro-4-(3-tosylprop-1-en-2-yl)benzene (3r).9g White
solid (123.3 mg, 85%); mp 108−110 °C; purification by silica gel
1
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.11); H NMR (400
(eluent: PE/EA = 20:1, Rf = 0.11); H NMR (400 MHz, CDCl3,
MHz, CDCl3, ppm) δ 7.65 (d, J = 8.24 Hz, 2H), 7.31−7.24 (m, 4H),
6.93 (t, J = 6.56 Hz, 2H), 5.53 (s, 1H), 5.17 (s, 1H), 4.21 (s, 2H),
2.40 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 162.5 (d, J =
247.8 Hz), 144.8, 135.7, 135.4, 135.0 (d, J = 3.3 Hz), 129.6, 128.6,
128.1 (d, J = 8.2 Hz), 121.7, 115.2 (d, J = 21.6 Hz), 62.3, 21.5.
1-Bromo-3-(3-((4-nitrophenyl)sulfonyl)prop-1-en-2-yl)benzene
(3s). Yellow oil (150.5 mg, 79%); purification by silica gel
ppm) δ 7.98 (dt, J = 1.96, 7.24 Hz, 2H), 7.65−7.59 (m, 1H), 7.58−
7.51 (m, 2H), 7.45−7.32 (m, 5H), 6.61 (d, J = 1.20 Hz, 1H), 2.53 (d,
J = 1.12 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 153.4,
142.1, 140.0, 133.1, 129.8, 129.2, 128.6, 127.3, 127.1, 126.2, 17.1.
(E)-1-Bromo-4-((2-phenylprop-1-en-1-yl)sulfonyl)benzene (4c).
Yellow oil (151.2 mg, 90%); purification by silica gel chromatography
1
(eluent: PE/EA = 20:1, Rf = 0.13); H NMR (400 MHz, CDCl3,
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.14); H NMR (400
ppm) δ 7.83 (dt, J = 1.92, 8.60 Hz, 2H), 7.69 (dt, J = 1.84, 8.60 Hz,
2H), 7.46−7.33 (m, 5H), 6.57 (d, J = 1.16 Hz, 1H), 2.52 (d, J = 1.16
Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 154.2, 141.2,
139.9, 132.5, 130.0, 128.8, 128.8, 128.4, 127.0, 126.3, 17.3. HRMS
(ESI-TOF) m/z: [M + K]+ calcd for C15H13BrO2SK 374.9451; found
374.9442.
MHz, CDCl3, ppm) δ 8.25 (dt, J = 2.20, 8.84 Hz, 2H), 7.92 (dt, J =
2.24, 8.84 Hz, 2H), 7.34 (dt, J = 1.20, 7.84 Hz, 1H), 7.21−7.14 (m,
2H), 7.15−7.07 (m, 1H), 5.64 (s, 1H), 5.36 (s, 1H), 4.31 (s, 2H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 150.7, 143.7, 140.1, 134.8,
131.3, 130.1, 130.1, 129.3, 124.9, 124.0, 123.9, 122.7, 62.1. HRMS
(ESI-TOF) m/z: [M + K]+ calcd for C15H12BrNO4SK 419.9302;
found 419.9285.
(E)-1-Fluoro-4-((2-phenylprop-1-en-1-yl)sulfonyl)benzene (4d).9b
Colorless oil (114.6 mg, 83%); purification by silica gel chromatog-
raphy (eluent: PE/EA = 20:1, Rf = 0.14); 1H NMR (400 MHz,
CDCl3, ppm) δ 8.03−7.93 (m, 2H), 7.43−7.32 (m, 5H), 7.27−7.19
(m, 2H), 6.58 (d, J = 1.20 Hz, 1H), 2.53 (d, J = 1.16 Hz, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 165.5 (d, J = 254.1 Hz),
4-(3-(Phenylsulfonyl)prop-1-en-2-yl)-1,1′-biphenyl (3t). Yellow
solid (155.4 mg, 93%); mp 106−108 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.12); H NMR (400
MHz, CDCl3, ppm) δ 7.87−7.76 (m, 2H), 7.59−7.52 (m, 3H), 7.50−
7.41 (m, 6H), 7.50−7.41 (m, 3H), 5.66 (s, 1H), 5.24 (s, 1H), 4.32 (s,
2H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 140.8, 140.3, 138.3,
137.5, 136.0, 133.6, 128.9, 128.8, 128.6, 127.5, 127.0, 126.9, 126.6,
121.7, 62.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C21H18O2SNa 357.0920; found 357.0904.
153.8, 140.1, 138.3, 130.1, 130.0 (d, J = 1.6 Hz), 128.8, 127.3, 126.3,
116.5 (d, J = 22.5 Hz), 17.2.
(E)-1-Methoxy-3-(1-(phenylsulfonyl)prop-1-en-2-yl)benzene
(4e).9i White solid (131.1 mg, 91%); mp 64−66 °C; purification by
1
silica gel chromatography (eluent: PE/EA = 15:1, Rf = 0.11); H
4-(3-Tosylprop-1-en-2-yl)-1,1′-biphenyl (3u).9c White solid (160.2
mg, 92%); mp 112−114 °C; purification by silica gel chromatography
NMR (400 MHz, CDCl3, ppm) δ 8.01−7.93 (m, 2H), 7.65−7.51 (m,
3H), 7.30−7.24 (m, 1H), 7.00−6.87 (m, 3H), 6.60 (d, J = 1.20 Hz,
1H), 3.80 (s, 3H), 2.51 (d, J = 1.20 Hz, 3H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 159.8, 153.4, 142.2, 141.6, 133.3, 129.8, 129.3,
127.6, 127.3, 118.7, 115.2, 112.2, 55.4, 17.3.
1
(eluent: PE/EA = 15:1, Rf = 0.15); H NMR (400 MHz, CDCl3,
ppm) δ 7.69 (d, J = 8.24 Hz, 2H), 7.62−7.53 (m, 2H), 7.52−7.41 (m,
4H), 7.40−7.32 (m, 3H), 7.22 (d, J = 7.96 Hz, 2H), 5.66 (s, 1H),
5.23 (s, 1H), 4.30 (s, 2H), 2.36 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3, ppm) δ 144.6, 140.7, 140.3, 137.5, 136.0, 135.3, 129.4, 128.7,
128.6, 127.4, 126.9, 126.9, 126.6, 121.6, 62.0, 21.5.
(E)-1-Methoxy-3-(1-tosylprop-1-en-2-yl)benzene (4f).20 White
solid (140.5 mg, 93%); mp 70−72 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.15); H NMR (400
MHz, CDCl3, ppm) δ 7.84 (d, J = 8.28 Hz, 2H), 7.34 (d, J = 8.12 Hz,
2H), 7.26 (t, J = 7.52 Hz, 1H), 7.02−6.84 (m, 3H), 6.59 (d, J = 0.96
Hz, 1H), 3.80 (s, 3H), 2.50 (d, J = 0.88 Hz, 3H), 2.43 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 159.7, 152.9, 144.2, 141.7,
4-(3-((4-Methoxyphenyl)sulfonyl)prop-1-en-2-yl)-1,1′-biphenyl
(3v). Yellow solid (167.5 mg, 92%); mp 118−120 °C; purification by
1
silica gel chromatography (eluent: PE/EA = 12:1, Rf = 0.13); H
NMR (400 MHz, CDCl3, ppm) δ 7.79−7.63 (m, 2H), 7.56 (d, J =
3.68 Hz, 2H), 7.50−7.40 (m, 4H), 7.39−7.30 (m, 3H), 6.91−6.81
(m, 2H), 5.65 (s, 1H), 5.24 (s, 1H), 4.29 (s, 2H), 3.77 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 163.6, 140.7, 140.3, 137.5,
136.3, 130.8, 129.8, 128.8, 127.5, 127.0, 126.9, 126.6, 121.6114.0,
62.3, 55.5. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C22H20O3SH
365.1206; found 365.1191.
139.3, 129.9, 129.8, 128.0, 127.3, 118.7, 115.1, 112.2, 55.4, 21.6, 17.3.
(E)-1-(1-((4-Bromophenyl)sulfonyl)prop-1-en-2-yl)-3-methoxy-
benzene (4g). Yellow oil (161.1 mg, 88%); purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.18); H NMR (400
MHz, CDCl3, ppm) δ 7.82 (dt, J = 2.24, 8.64 Hz, 2H), 7.69 (dt, J =
1.72, 8.64 Hz, 2H), 7.29 (d, J = 7.96 Hz, 1H), 7.00−6.86 (m, 3H),
6.57 (d, J = 1.20 Hz, 1H), 3.81 (s, 3H), 2.50 (d, J = 1.16 Hz, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 159.8, 154.1, 141.5, 141.2,
132.6, 132.5, 129.9, 128.8, 127.1, 118.7, 115.3, 112.2, 55.4, 17.4.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C16H15BrO3SNa
388.9817; found 388.9805.
4-(3-((4-Bromophenyl)sulfonyl)prop-1-en-2-yl)-1,1′-biphenyl
(3w). Yellow oil (183.4 mg, 89%); purification by silica gel
1
chromatography (eluent: PE/EA = 15:1, Rf = 0.16); H NMR (400
MHz, CDCl3, ppm) δ 7.66−7.51 (m, 6H), 7.50−7.41 (m, 4H), 7.40−
7.27 (m, 3H), 5.67 (s, 1H), 5.27 (s, 1H), 4.32 (s, 2H). 13C{1H} NMR
4023
https://dx.doi.org/10.1021/acs.joc.0c02869
J. Org. Chem. 2021, 86, 4018−4026

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
(E)-1-Bromo-3-(1-(phenylsulfonyl)prop-1-en-2-yl)benzene
23.8, 13.2. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H15BrO2SNa 372.9868; found 372.9868.
(4h).7a White solid (151.2 mg, 90%); mp 82−84 °C; purification by
1
silica gel chromatography (eluent: PE/EA = 20:1, Rf = 0.13); H
NMR (400 MHz, CDCl3, ppm) δ 8.00−7.92 (m, 2H), 7.64−7.60 (m,
1H), 7.60−7.54 (m, 2H), 7.53−7.46 (m, 2H), 7.31 (dt, J = 1.40, 7.76
Hz, 1H), 7.25−7.20 (m, 1H), 6.58 (q, J = 1.28 Hz, 1H), 2.51 (d, J =
1.24 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 151.8,
142.3, 141.9, 133.5, 132.8, 130.3, 129.4, 129.3, 128.6, 127.3, 125.0,
122.9, 17.2.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.0c02869.
■
sı
NMR spectra data of the compounds, other optimization
of reaction conditions, and the copy of HRMS data
(PDF)
(E)-1-Nitro-3-(1-tosylprop-1-en-2-yl)benzene (4i).9i Yellow oil
(139.5 mg, 88%); purification by silica gel chromatography (eluent:
1
PE/EA = 20:1, Rf = 0.12); H NMR (400 MHz, CDCl3, ppm) δ
8.22−8.21 (m, 2H), 7.86 (d, J = 8.28 Hz, 2H), 7.71 (d, J = 7.88 Hz,
1H), 7.58−7.56 (m, 1H), 7.37 (d, J = 8.04 Hz, 2H), 6.65 (d, J = 0.76
Hz, 1H), 2.58 (d, J = 1.12 Hz, 3H), 2.45 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3, ppm) δ 149.9, 148.4, 144.8, 142.0, 138.6, 132.2, 130.3,
130.1, 129.9, 127.5, 124.3, 121.3, 21.6, 17.2.
AUTHOR INFORMATION
Corresponding Author
■
Yunfeng Chen − School of Chemistry and Environmental
Engineering, Wuhan Institute of Technology, Wuhan 430205,
P. R. China; orcid.org/0000-0002-6220-5015;
Email: yfchen@wit.edu.cn
(E)-4-(1-(Phenylsulfonyl)prop-1-en-2-yl)-1,1′-biphenyl (4j). Yel-
low oil (152.0 mg, 91%); purification by silica gel chromatography
1
(eluent: PE/EA = 20:1, Rf = 0.13); H NMR (400 MHz, CDCl3,
ppm) δ 8.01−7.99 (m, 2H), 7.62−7.59 (m, 7H), 7.57−7.47 (m, 4H),
7.37 (t, J = 7.16 Hz, 1H), 6.69 (d, J = 1.08 Hz, 1H), 2.58 (d, J = 0.96
Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 153.0, 142.9,
142.3, 139.9, 138.8, 133.3, 129.3, 129.0, 127.9, 127.4, 127.3, 127.2,
127.1, 126.8, 17.1. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H18O2SNa 335.1100; found 335.1101.
Authors
Ye Wang − School of Chemistry and Environmental
Engineering, Wuhan Institute of Technology, Wuhan
430205, P. R. China
Guowei Xiong − School of Chemistry and Environmental
Engineering, Wuhan Institute of Technology, Wuhan
430205, P. R. China
Chuanxin Zhang − School of Chemistry and Environmental
Engineering, Wuhan Institute of Technology, Wuhan
430205, P. R. China
(E)-2-(1-Tosylprop-1-en-2-yl)naphthalene (4k). White solid
(144.9 mg, 90%); mp 124−126 °C; purification by silica gel
1
chromatography (eluent: PE/EA = 20:1, Rf = 0.14); H NMR (400
MHz, CDCl3, ppm) δ 7.93−7.89 (m, 3H), 7.85−7.82 (m, 3H), 7.54−
7.51 (m, 3H), 7.40−7.38 (m, 2H), 6.77 (s, 1H), 2.66 (s, 3H), 2.47 (s,
3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ 152.8, 144.2, 139.4,
137.4, 133.8, 133.0, 129.9, 128.6, 128.5, 128.1, 127.6, 127.4, 127.2,
126.8, 126.3, 123.5, 21.6, 17.2. HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C20H18O2SNa 345.0920; found 345.0905.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c02869
(E)-2-(1-((4-Bromophenyl)sulfonyl)prop-1-en-2-yl)naphthalene
Notes
(4l). Yellow oil (167.9 mg, 87%); purification by silica gel
1
The authors declare no competing financial interest.
chromatography (eluent: PE/EA = 20:1, Rf = 0.15); H NMR (400
MHz, CDCl3, ppm) δ 7.91−7.79 (m, 6H), 7.77−7.67 (m, 2H), 7.53−
7.46 (m, 3H), 6.72 (d, J = 1.16 Hz, 1H), 2.63 (d, J = 1.16 Hz, 3H).
13C{1H} NMR (100 MHz, CDCl3, ppm) δ 154.0, 141.3, 137.1, 133.9,
132.9, 132.6, 132.3, 130.1, 128.9, 128.6, 127.7, 127.4, 127.3, 126.9,
126.4, 123.4, 17.3. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C19H15BrO2SNa 408.9868; found 408.9883.
ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
China (21002076) and the Graduate Innovative Fund of
Wuhan Institute of Technology (CX2019166).
(E)-((2-Phenylbut-1-en-1-yl)sulfonyl)benzene (4m).18 Yellow oil
(119.7 mg, 88%); purification by silica gel chromatography (eluent:
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(E)-1-Methyl-4-((2-phenylbut-1-en-1-yl)sulfonyl)benzene (4n).15a
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1
(eluent: PE/EA = 20:1, Rf = 0.11); H NMR (400 MHz, CDCl3,
ppm) δ 7.83 (dd, J = 8.08, 8.24 Hz, 2H), 7.39−7.33 (m, 7H), 6.46 (s,
1H), 3.06 (q, J = 7.48 Hz, 2H), 2.43 (s, 3H), 0.97 (t, J = 7.48 Hz,
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1
(eluent: PE/EA = 20:1, Rf = 0.13); H NMR (400 MHz, CDCl3,
ppm) δ 7.84 (dt, J = 2.36, 8.68 Hz, 2H), 7.69 (dt, J = 2.32, 8.68 Hz,
2H), 7.40−7.35 (m, 5H), 6.44 (s, 1H), 3.05 (q, J = 7.48 Hz, 2H),
0.99 (t, J = 7.48 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, ppm) δ
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4024
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pubs.acs.org/joc
Article
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