Allylic C-S Bond Construction through Metal-Free Direct Nitroalkene Sulfonation

Article abstract of DOI:10.1021/acs.joc.7b02595

A metal-free, open-flask protocol was developed for the preparation of allylic sulfones through direct condensation of sodium arylsulfinates and β,β-disubstituted nitroalkenes. The key step of this process was the Lewis base-promoted equilibrium between nitroalkenes and allylic nitro compounds. Through this process, the readily available conjugated nitroalkenes can be easily converted into allylic nitro compounds, which contain more reactive C=C bonds toward the sulfonyl radical addition. As a result, allylic sulfones were prepared in excellent yields with a broad substrate scope under mild conditions.

Full text of DOI:10.1021/acs.joc.7b02595

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Article
Allylic C-S Bond Construction through
Metal-Free Direct Nitroalkene Sulfonation
Xue Lei, Lei Zheng, Chuanxin Zhang, Xiaodong Shi, and Yunfeng Chen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b02595 • Publication Date (Web): 22 Jan 2018
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Allylic C-S Bond Construction through Metal-Free Direct
Nitroalkene Sulfonation
8
Xue Lei,† Lei Zheng,† Chuanxin Zhang,† Xiaodong Shi*,‡ and Yunfeng Chen*,†
†School of Chemistry and Environmental Engineering, Wuhan Institute of Technology,
Wuhan 430073, P. R. China.
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‡The Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, Tampa,
Florida 33620, United States
DMSO
less reactive
NO2
+
ArSO2Na
SO2Ar
R
R
C=C
100 oC
R
fast equillibrium
metal-free;
open-flask practical conditions
> 25 examples, up to 95% yield
more reactive
C=C
NO2
ABSTRACT
A metal-free, open-flask protocol was developed for the preparation of allylic sulfones
through direct condensation of sodium arylsulfinates and a,b-disubstituted nitroalkenes. The
key step of this process was the Lewis base promoted equilibrium between nitroalkenes and
allylic nitro compounds. Through this process, the readily available conjugated nitroalkenes
can be easily converted into allylic nitro compounds, which contain more reactive C=C bond
towards sulfonyl radical addition. As a result, allylic sulfones were prepared in excellent
yields with a broad substrate scope under mild conditions.
INTRODUCTION
One of the general goals of synthetic methodology research is to develop new approaches for
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important chemical bond construction with high chemical efficiency and practical operation
protocols. 1 Due to the significant role of sulfur-containing compounds in chemical, 2
biological, 3 and medicinal research, 4 more and more attention has been paid to the
development of efficient new approaches to construct C-S bond in recent years.5 Allyl
sulfones are interesting and versatile sulfur-containing building blocks in organic synthesis.6
With the electron-withdrawing RSO2 moiety, allyl sulfones can serve as synthons for many
useful transformations.7 The general synthetic strategy of allyl sulfone synthesis can be
divided into two major approaches: A) two-electron nucleophilic addition and B) sulfonyl
radical addition.
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As shown in Scheme 1A, one popular method for synthesis of allyl sulfones is the Tsuji-Trost
reaction, especially under Pd or Ir-catalyzed nucleophilic addition to metal π-allyl
intermediates.8,9 Although these occur with overall good reaction scope, this transformation
usually requires exquisite condition control in order to avoid catalyst deactivation caused by
sulfur coordination.10 In recent years, sulfonyl radical-mediated reactions have gained more
and more attention due to its good reactivity toward C-C multiple bonds and ability to avoid
undesired side reactions.11 In fact, this strategy has been applied to allyl sulfone synthesis.12
Two representative examples are shown in Scheme 1B.
Scheme 1. General Synthetic Strategy for Allyl Sulfones
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(A) Tsuji-Trost reaction
5
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R
cat [M]
-
R
SO2Ar
R
LG
ArSO2
+
7
8
[M]
two-electron process
(B) Sulfonyl radical addition
O
9
20% TBAI,
2 equiv TBHP
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Ar S NHNH2
O
+
SO2Ar
CH3CN, 80 oC, 20 h
R
R
ref 12a
5% TBA2-eosin Y;
20% Co(dmgH)2pyCl;
O
+
SO2Ar
Ar S OH
R
R
2 equiv pyridine
CHCl3, green LED, Ar
ref 12b
- H+
SO2Ar
photocatalyst
[O]
O
S
O
Ar
Ar S O
R
A
O
In 2012, Li and coworkers reported the application of sulfonyl hydrazine as a radical
precursor and TBHP (tert-butyl hydroperoxide) (2 equiv) as oxidant.12a Under TBAI
(tetrabutylammonium iodide) catalytic conditions, allyl sulfones were formed in modest to
good yields. Another important recent development was the direct condensation of sulfinic
acids and alkenes with the combination of photocatalyst and metal catalysts reported by Lei
and coworkers.12b TBA2-eosin Y was applied as an effective photocatalyst to initiate the
formation of sulfonyl radicals. Sequential radical addition and Co(dmgH)2pyCl catalyzed
dehydrogenation produced the desired allyl sulfones without additional external oxidants.
This seminal work revealed one important reaction perspective which was that sulfonyl
radicals can be formed directly from sulfinic acids under proper conditions with high
efficiency. The major drawback of this process was the requirement of strict degassing and
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argon protection, which made the process less practical. Herein, we report a direct
condensation of sodium arylsulfinates and nitroalkenes for the synthesis of allyl sulfones.
Notably, this reaction not only provided allyl sulfones in moderate to high yield, but also was
performed in open-flask, and metal-free conditions, highlighting the efficiency and
practicality of this strategy.
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Our interest in developing new methods for the preparation of allyl sulfones was initiated
from the Lewis base catalyzed nitroalkene activation previously conducted in our group.13
In those studies, the designated β-elimination was employed to promote challenging
intermolecular cascade condensation from competing reaction equilibrium. While
nitroalkenes are good Lewis base receptors (two-electron receptor),14 we were wondering
whether this highly electron-deficient C=C double bonds (compared with regular alkene)
would react with radicals. Notably, sulfonyl radical is also electron deficient. Thus, it is
expected that harsh conditions or strong oxidants are required to promote this transformation.
Two examples are shown in Scheme 2A. 15 According to literature, sulfonylation of
nitroalkenes can be achieved in the presence of strong oxidants. For example, with a silver
catalyst (20%) and using K2S2O8 (2 equiv.) as oxidant, the desired vinyl sulfones can be
prepared.15a However, N2 protection was required to avoid formation of oxidative side
products. Recently, we reported the application of Mn(OAc)3 as the oxidant to achieve the
same transformation.15b In this case, inert atmosphere was not necessary, which made the
process more practical. Based on the proposed reaction mechanism, both examples produced
radical intermediate B. It is reasonable to assume that the most challenging step in both
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reactions is the sulfonyl radical addition towards electron deficient nitroalkenes. Although
the elimination step remains unclear (through either NO2 anion or NO2 radical), the oxidation
of radical B is not likely involved to form carbocation, as occurring in the direct alkene
sulfonylation examples shown in Scheme 1B. Based on this analysis, we postulated the
reaction of β-disubstituted nitroalkene 1a with sodium arylsulfinates as a plausible new
reaction path towards the synthesis of allyl sulfone 3 as shown in Scheme 2B.
Scheme 2. Sulfonyl Radical Addition to Nitroalkene
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(A) Radical toward electrondeficient nitroalkene:Strong oxidants are required
conditions
NO2
SO2Ar
+
ArSO2Na
Ph
Ph
-
- NO2
or
- NO2
elimination?
easy
oxidation
"hard"
addition
NO2
ArSO2
Ph
easy
SO2Ar
B
condition 1: 20% AgNO3, 2 equiv K2S2O8, DMF, rt, N2 protection, ref 15a;
condition 2: 3 equiv Mn(OAc)3, DMF,100 oC, open flask, ref 15b;
(B) Proposed synthesis of allyl sulfone from β-substituted nitroalkene
Lewis
Base
ArO2S
ArO2S
Ph
Ph
ArSO2
Ph
NO2
Ph
NO2
NO2
1a
1a’
1) easier radical addition to 1a' than 1a;
2) rapid NO2 elimination of intermediate C (easier than A oxidation)
3
C
It is clear the sulfonyl radical addition will be feasible on allylic compound 1a' with more
electron rich C=C double bond, giving radical intermediate C. Elimination of NO2 (similar to
intermediate B) will afford the desired allyl sulfone 3. Compared with the dehydrogenation
approach,12b this new route successfully avoids the oxidation of radical to carbocation, which
permits higher overall efficiency with potentially milder conditions (no need for second
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oxidants or dehydrogenation catalyst). Moreover, although the allylic compound 1a' is not
easy to prepare (compared with nitroalkene 1a), we have demonstrated the fast equilibrium
between these two compounds with the presence of a Lewis base catalyst.16 Since sulfinate
salt can serve as a mild base, it will be expected that the same equilibrium should be
established under the reaction conditions.
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RESULTS AND DISCUSSION
To testify our hypothesis, reactions between nitroalkene 1a and sodium p-toluenesulfinate 2a
were performed under various conditions (Table 1).
Table 1. Reaction Conditions Screening a
conditions
+
ArSO2Na
NO2
SO2Ar
SO2Ar
Ar = Tol
Ph
Ph
Ph
1a
2a
3a
4a
convn
1a
yieldb
3a
yieldb
4a
entry
reaction conditions
3 equiv Mn(OAc)3, DMF, 100 oC, 4 h
1
2
3
58%
95%
40%
10%
trace
10%
27%
10% TBAI, 2 equiv TBHP, CH3CN, 80 oC, 4 h
0
0
20% AgNO3, 2 equiv K2S2O8, DMF, rt, Ar, 4h
4
5
20% AgNO3, DMSO, 100 oC, 4 h
DMSO, 100 oC, 4 h
100%
100%
75%
75%
88%
50%
35%
12%
90%
6%
trace
trace
trace
0
6
DMSO, 80 oC, 4 h
7
DMSO, 100 oC, 4 h, Ar, (degassed)
100% I2, DMSO, 80 oC, 4 h
10% I2, 2 equiv. TBHP, DMSO, 80 oC, 2 h
Other conditions (see SI)
50%
8
44%
9
100%
0
10
aReaction conditions: 1a (0.3 mmol, 1 equiv.), 2a (1.5 equiv.), catalyst (mol %), oxidant (equiv.) in
b
DMSO (3.0 mL), open air. Isolated yield. DMF = dimethylformamide, DMSO = dimethyl
sulfoxide.
Very low yields of desired products were observed with poor chemoselectivity (entries 1-3)
when we used previously reported conditions. These results clearly revealed the different
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reactivity between regular nitroalkene and a, b-alkyl-nitroalkene under these radical addition
conditions. Our breakthrough was from two unexpected control experiments: 1) using
catalytic amount (20%) AgNO3 resulted in the formation of allyl sulfone 3a in 75% and vinyl
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o
sulfone 4a in 6%, and 2) simply treating reaction mixtures with DMSO at 100 C (without
any catalyst) gave the desired allyl sulfone 3a in 88% yield (entry 5). Notably, excellent
regioselectivity was obtained with trace amount of vinyl sulfone 4a formed under this simple
condition. Conducting the reaction under oxygen-free conditions (entry 7) gave a lower yield,
which suggested the important role of oxygen in the formation of sulfinic radical under this
catalyst-free condition. Reducing reaction temperature to 80 oC gave significantly lower yield,
likely due to the competing sulfinate oxidation side reaction. To enhance the formation of
sulfinic radical process, 10% I2 along with TBHP as the oxidant was tested. As expected, 3a
was formed in excellent yield (90% isolated yield) even at lower temperature (entry 9).17
Compared with the catalyst-free conditions, the I2/TBHP conditions gave much cleaner
reaction with 3a as the only product observed in crude NMR. It is important to note that
application of 1 equiv I2 will quench the reaction significantly (entry 8). Monitoring reaction
confirmed that no formation of allylic nitro compound 1a' if 1 equiv of I2 was used, because
I2 will react with arylsulfinate salt and cause almost no formation of 1a' for sulfonyl radial
addition. With the two optimal conditions revealed, we evaluated the reaction scope. The
results are summarized in Figure 1.
Figure 1. Substrate Scopea, b
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R
NO2
R
SO2Ar
3 or 5
conditions
ArSO2Na
+
Ar
Ar
1
2
7
8
9
O O
S
R1 = H, 3b, 88% (85%)
R1 = OMe, 3c, 92% (89%)
R1 = F, 3d, 80% (72%)
R1 = Cl, 3e, 85% (80%)
R1 = Br, 3f, 83% (77%)
Ph
Ar
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R1
O O
S
Ar = p-OMe-C6H4
R1=F, 3i, 85% (82%)
R1 = OMe, 3g, 95% (92%) R1=Cl, 3j, 78% (75%)
R1=Br, 3k, 85% (81%)
R1 = CH3, 3h, 90% (87%)
R1
Ar = p-Br-C6H4
Ar = p-F-C6H4
R1 = H, 3p, 76% (72%)
R1 = CH3, 3q, 78% (75%) R1 = CH3, 3t, 93% (90%)
R1 = OMe, 3r, 85% (80%) R1 = F, 3u, 86% (82%)
Ar = p-Me-C6H4
R1 = H, 3s, 88% (85%)
R1 = OMe, 3l, 87% (83%)
R1 = CH3, 3m, 85% (78%)
R1 = Cl, 3n, 82% (75%)
R1 = F, 3o, 78% (71%)
O O
S
R1 = H, 3v, 88% (85%)
S
R1 = CH3, 3w, 93% (90%)
R1 = OMe, 3x, 95% (92%)
R1
5a, Ar=Ph, Z/E = 2.5:1, 85% (81%);
5b, Ar=p-F-C6H4, Z/E = 3:1, 79% (76%);
5c, Ar=p-Cl-C6H4, Z/E = 10:1, 74% (70%);
SO2Ar
SO2Ar
6 (trace)
Ph
Ph
5
a Reaction conditions: nitroolefins (0.3 mmol), sodium sulfinates (0.45 mmol), I2 (0.03 mmol), TBHP
(0.6 mmol), DMSO (3 mL), 80 °C, 2 h, open air. Reaction conditions in parentheses: nitroolefins (0.3
mmol), sodium sulfinates (0.45 mmol), DMSO (3 mL), 100 °C, 4 h, open air. b Isolated yield.
In summary, all substrates tested gave good yields under both conditions, while the TBHP/I2
system provided slightly better yield and faster reaction rate. An array of sodium
arylsulfinates with both electron-donating and electron-withdrawing groups on the phenyl
ring have been tested, and satisfactory yields were obtained. Investigations on different nitro-
olefins showed that the nitro-olefins with electron-donating group (R2 = OMe, 3g-k; Me, 3s-
u) gave higher yields than those with electron-withdrawing group (R2 = F, 3p-r). Notably,
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heterocyclic containing nitro-olefins also give the corresponding products in good yields (3v-
x). Furthermore, α-ethyl nitro-olefins were also tested for this reaction (5a-b). According to
the structure of substrate and the mechanism we proposed above, compound 6 was expected.
However, under standard reaction conditions, compound 5 was obtained in all cases, which
involved a sequential sulfonyl radical additions.18 The isolated yield of (2-phenylbut-2-
enylsulfonyl)benzene 5a (Z isomer and E isomer) was up to 85%, and the Z/E ratio was up to
10:1 for sodium 4-chlorobenzenesulfinate. Although the Z/E ratio was not very high for some
cases, the high regioselectivity and good yield made this transformation a good option for the
synthesis of the similar multi-substituted allyl sulfones.
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To further explore the substrate scope of the reaction, (nitromethylene)cyclohexane was
reacted with sodium sulfinates (Figure 2A). However, no sulfonation products were observed
under either thermal or oxidation conditions. Instead, we found the reaction worked well with
I2 (0.1 equiv.) at 80 oC for 8h and product 7a-7d were obtained. Product 7a was selected as
the representative compound and characterized by X-ray crystallography, as shown in Figure
2A.
Figure 2. Aliphatic Substrates and reaction profile
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(A)
NO2
NO2
I2 10 mol%
+
ArSO2Na
DMSO, 80 oC
SO2Ar
7
7a: Ar = Ph, 39%a; 7b: Ar = Tol, 41%;
7c: Ar = p-OMe-C6H4, 45%; 7d: Ar = p-Br-C6H4, 34%
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X-Ray crystal of 7a
(B)
Thermal or Radical
condition
TEMPO (4 equiv.)
Ph
+
NO2
SO2Tol
+
TolSO2Na
Ph
1a’, >95%
Ph
NO2
3a, 0%
1a
(C)
NO2
+
+
SO2Tol
+
1a
2a
NO2
SO2Tol
Ph
Ph
Ph
1a'
3a
8
X-Ray crystal of 8
d
l
e
Y
i
Reaction Time (min)
Reaction conditions: nitroolefins (0.3 mmol), sodium sulfinates (0.45 mmol), I2 (0.03 mmol), TBHP
(0.6 mmol), DMSO, 80 oC, open air.
A radical trapping experiment was performed to support the radical mechanism (Figure 2B).
The reaction with a stoichiometric amount of radical inhibitor (TEMPO) was performed
under two optimal conditions (either DMSO at 100 oC or 10% I2/TBHP at 80 oC). Notably,
only the conversion of 1a to 1a' was observed, while desired product 3a was not detected.
This result implied the further step involved a free radical process. Furthermore, the time-
1
dependent reaction profile of 1a with sodium p-tolylsulfinate was obtained using H NMR
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(Figure 2C). The Lewis base-promoted equilibrium between 1a and 1a' occurred within 20
min. The product 3a was formed accompanied by a small amount of 8 (confirmed by X-ray
crystallography). Intermediate 8 could also slowly convert into desired product 3a based on
our experimental observation. Addition of 100% I2 inhibited the formation of allylic
compound 1a' (see SI). Overall, these observations verified the mechanism we proposed.
CONCLUSION
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In conclusion, we report here a metal-free direct nitroalkene sulfonylation reaction between
sodium arylsulfinates and α, β-disubstituted nitroalkenes. This method can give allyl sulfones
with high efficiency. By tuning the substituents on both reactants, the allyl sulfones can be
obtained in high selectivity and yield. Further mechanistic studies as well as synthetic
application of this transformation are the focus of ongoing investigations.
EXPERIMENTAL SECTION
General Information. Unless otherwise noted, all reagents were purchased from commercial
suppliers and used without further purification. 1H NMR and 13C NMR spectra were recorded
on a Bruker AscendTM 600 or Bruker AV400 spectrometers. Chemical shifts were reported
relative to internal tetramethylsilane (TMS) (0.00 ppm) or CDCl3 (7.26 ppm) for 1H, CDCl3
(77.0 ppm) for 13C. Flash column chromatography was performed on 200-300 mesh silica gel.
Mass analysis was performed in a Waters Xevo G2 QTOFMS mass spectrometer. A high
resolution TOFMS with an ESI source was used to detect the analytes of interest in positive
mode or negative mode. Melting points were measured on a melting point tester RY-1G
apparatus and uncorrected.
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The general procedure to synthesize nitroalkenes19,20,21
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Synthesis of (E)-β-aryl-β -methyl nitroalkenes.
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(E)-(1-nitroprop-1-en-2-yl)benzene (1a).21a Yellow oil (6.8 g, 50% yield). Eluent: Petroleum
ether. 1H NMR (500 MHz, CDCl3, ppm) δ 7.44 (s, 5H), 7.29 (d, J = 1.0 Hz, 1H), 2.63 (d, J =
1.5 Hz, 3H). 13C NMR (125 MHz, CDCl3, ppm) δ 149.8, 138.1, 136.2, 130.3, 128.9, 126.7,
18.4.
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(E)-1-methoxy-4-(1-nitroprop-1-en-2-yl)benzene (1b).21a Yellow oil (6.2 g, 48% yield).
Eluent: Petroleum ether. 1H NMR (400 MHz, CDCl3, ppm) δ 7.43 (d, J = 8.8 Hz, 2H), 7.33
(d, J = 1.2 Hz, 1H), 6.95 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), 2.63 (d, J = 1.2 Hz, 3H). 13C NMR
(100 MHz, CDCl3, ppm) δ 161.6, 149.7, 135.1, 130.1, 128.4, 114.4, 55.4, 18.3.
(E)-1-bromo-4-(1-nitroprop-1-en-2-yl)benzene (1c).21a Yellow oil (5.5 g, 45% yield). Eluent:
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Petroleum ether. H NMR (500 MHz, CDCl3, ppm) δ 7.60 - 7.56 (m, 2H), 7.34 - 7.31 (m,
2H), 7.28 (d, J = 1.5 Hz, 1H), 2.62 (d, J = 1.5 Hz, 3H). 13C NMR (125 MHz, CDCl3, ppm) δ
148.6, 137.2, 136.4, 132.3, 128.4, 124.9, 18.4.
(E)-1-fluoro-4-(1-nitroprop-1-en-2-yl)benzene (1d).21a Yellow oil (5.7 g, 43% yield). Eluent:
Petroleum ether. 1H NMR (500 MHz, CDCl3, ppm) δ 7.48 - 7.43 (m, 2H), 7.28 (d, J = 1.5 Hz,
1H), 7.13 (t, J = 8.5 Hz, 2H), 2.63 (d, J = 1.5 Hz, 3H). 13C NMR (125 MHz, CDCl3, ppm) δ
164.0 (d, J = 251.7 Hz), 148.7, 136.2, 134.3, 128.8 (d, J = 8.5 Hz), 116.2 (d, J = 21.9 Hz),
18.6.
(E)-1-methyl-4-(1-nitroprop-1-en-2-yl)benzene (1e).21b Yellow oil (7.2 g, 55% yield). Eluent:
Petroleum ether. 1H NMR (400 MHz, CDCl3, ppm) δ 7.36 (d, J = 8.4 Hz, 2H), 7.31 (d, J =
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1.2 Hz, 1H), 7.24 (d, J = 8.0 Hz, 2H), 2.63 (d, J = 1.2 Hz, 3H), 2.39 (s, 3H). 13C NMR (100
MHz, CDCl3, ppm) δ 149.9, 140.8, 135.7, 135.2, 129.7, 126.7, 21.2, 18.3.
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(E)-2-(1-nitroprop-1-en-2-yl)thiophene (1f).21c Yellow oil (7.8 g, 58% yield). Eluent:
Petroleum ether. 1H NMR (400 MHz, CDCl3, ppm) δ 7.57 (s, 1H), 7.49 - 7.46 (m, 2H), 7.13
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(t, J = 4.4 Hz, 1H), 2.70 (s, 3H). C NMR (100 MHz, CDCl3, ppm) δ 142.9, 140.5, 133.7,
129.6, 129.2, 128.6, 17.9.
(E)-(1-nitrobut-1-en-2-yl)benzene (1g).21b Yellow oil (6.9 g, 52% yield). Eluent: Petroleum
ether. 1H NMR (400 MHz, CDCl3) δ 7.51 - 7.43 (m, 5H), 7.22 (s, 1H), 3.12 (q, J = 7.6 Hz,
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2H), 1.19 (t, J = 7.6 Hz, 3H). C NMR (100 MHz, CDCl3) δ 155.7, 137.0, 135.7, 130.2,
129.0, 127.1, 24.7, 12.7.
(3-nitroprop-1-en-2-yl)benzene (1a').21d Yellow oil (8 g, 80% yield). Eluent: Petroleum ether.
1H NMR (500 MHz, CDCl3, ppm) δ 7.45-7.43 (m, 2H), 7.40 - 7.33 (m, 3H), 5.83 (s, 1H),
5.54 (s, 1H), 5.37 (s, 2H). 13C NMR (125 MHz, CDCl3, ppm) δ 137.9, 136.0, 128.8, 128.8,
125.8, 121.8, 79.6.
Synthesis of (nitromethylene)cyclohexane.
(nitromethylene)cyclohexane (1h) and 1-(nitromethyl)cyclohex-1-ene (1h').20b, 21e Yellow oil.
(6.5 g, 45% yield). Eluent: Petroleum ether. 1H NMR (400 MHz, CDCl3, ppm) 1h δ 6.89 (s,
1H), 2.86 - 2.81 (m, 2H), 2.22 - 2.17 (m, 2H), 1.73 - 1.58 (m, 6H). 1h' δ 5.92 (s, 1H) 4.78 (s,
2H), 2.13 - 2.03 (m, 4H), 1.73 - 1.58 (m, 4H).
The procedure for the synthesis of allyl sulfones: The solution of nitroolefins 1a-1g (0.3
mmol) and sodium sulfinates 2 (0.45 mmol) in DMSO (3 mL), was added I2 (10% mmol)，
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TBHP (0.6 mmol), the mixture was stirring at 80 C for 2 h. After the completion of the
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reaction, the mixture was poured into water, and extracted by ethyl acetate, washed with NaCl
(aq), dried with anhydrous Na2SO4, then the solvent was removed under reduced pressure to
obtain crude product, further purification by column chromatography on silica gel (Petroleum
ether:EtOAc = 20/1 to 10/1) gave allyl sulfones.
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The solution of nitroolefins 1a-1g (0.3 mmol) and sodium sulfinates 2 (0.45 mmol) in DMSO
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(3 mL) was stirred at 100 C for 4 h. After the completion of the reaction, the mixture was
poured into water, and extracted by ethyl acetate, washed with NaCl (aq), dried with
anhydrous Na2SO4, then the solvent was removed under reduced pressure to obtain crude
product, further purification by column chromatography on silica gel (Petroleum ether-
EtOAc: 20/1 to 10:1) gave allyl sulfones.
1-methyl-4-((2-phenylallyl)sulfonyl)benzene (3a).12a White solid (71.9 mg, 88% yield; 73.5
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mg, 90% yield). Mp: 97-98 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10). H NMR (600
MHz, CDCl3, ppm) δ 7.64 (d, J = 7.8Hz, 2H), 7.28 - 7.17 (m, 7H), 5.56 (s, 1H), 5.19 (s, 1H),
4.23 (s, 2H), 2.36 (s, 3H). 13C NMR (150 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).12a White solid (65.9 mg, 85% yield; 68.2 mg, 88%
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yield). Mp: 45-47 C. Eluent: EtOAc/Petroleum ether (V/V = 1:10). H NMR (600 MHz,
CDCl3, ppm) δ 7.77 (d, J = 7.8 Hz, 2H), 7.52 (t, J = 7.2 Hz, 1H), 7.40 (t, J = 7.8 Hz, 2H),
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7.27 - 7.20 (m, 5H), 5.57 (s, 1H), 5.20 (s, 1H), 4.26 (s, 2H). C NMR (150 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.
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1-methoxy-4-((2-phenylallyl)sulfonyl)benzene (3c).12b Yellow oil (77.0 mg, 89% yield; 79.6
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mg, 92% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10) H NMR (600 MHz, CDCl3,
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5.19 (s, 1H), 4.23 (s, 2H), 3.80 (s, 3H). C NMR (150 MHz, CDCl3, ppm) δ 163.6, 138.8,
136.7, 130.7, 129.8, 128.3, 127.9, 126.1, 121.6, 114.0, 62.2, 55.6.
1-fluoro-4-((2-phenylallyl)sulfonyl)benzene (3d). White solid (59.7 mg, 72% yield; 68.2 mg,
66.3% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (600 MHz, CDCl3, ppm)
δ 7.76 (dd, J = 8.4, 4.8 Hz, 2H), 7.23 (s, 5H), 7.07 (t, J = 8.4 Hz, 2H), 5.60 (s, 1H), 5.24 (s,
1H), 4.28 (s, 2H). 13C NMR (150 MHz, CDCl3) 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.
HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C15H13FO2SNa: 299.0512, found 299.0515.
1-chloro-4-((2-phenylallyl)sulfonyl)benzene (3e).21f White solid (70.2 mg, 80% yield; 74.7
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mg, 85% yield). Mp: 117-118 C. Eluent: EtOAc/Petroleum ether (V/V = 1:10). H NMR
(600 MHz, CDCl3, ppm) δ 7.66 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 7.27 - 7.19 (m,
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5H), 5.59 (s, 1H), 5.23 (s, 1H), 4.27 (s, 2H). C NMR (150 MHz, CDCl3, ppm) δ 140.3,
138.4, 136.7, 136.4, 130.1, 129.1, 128.4, 128.1, 126.1, 122.0, 62.2.
1-bromo-4-((2-phenylallyl)sulfonyl)benzene (3f).12a White solid (77.9 mg, 77% yield; 84.0
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mg, 83% yield). Mp: 127-128 C. Eluent: EtOAc/Petroleum ether (V/V = 1:10). H NMR
(600 MHz, CDCl3, ppm) δ 7.58 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.21 (s, 5H),
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5.58 (s, 1H), 5.22 (s, 1H), 4.26 (s, 2H). C NMR (150 MHz, CDCl3, ppm) δ 138.3, 137.1,
136.2, 132.0, 130.0, 128.8, 128.3, 128.0, 126.0, 122.0, 62.0.
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1-methoxy-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3g). Yellow oil (87.9 mg, 92%
yield; 90.7 mg, 95% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (400 MHz,
CDCl3, ppm) δ 7.71 - 7.66 (m, 2H), 7.25 - 7.19 (m, 2H), 6.91 - 6.84 (m, 2H), 6.80 - 6.74 (m,
2H), 5.49 (s, 1H), 5.07 (s, 1H), 4.21 (s, 2H), 3.83 (s, 3H), 3.78 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm) δ 163.6, 159.5, 136.2, 131.3, 130.8, 130.1, 127.4, 119.8, 114.0, 113.7, 62.5,
55.6, 55.2. HRMS (ESI-TOF) m/z [M + H]+ calcd. for C17H19O4S: 319.0999, found 319.1006.
1-methoxy-4-(3-tosylprop-1-en-2-yl)benzene (3h).12a White solid (78.9 mg, 87% yield; 81.6
mg, 90% yield). Mp: 62-63 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (400
MHz, CDCl3, ppm) δ 7.65 (d, J = 8.2 Hz, 2H), 7.22 (t, J = 6.0 Hz, 4H), 6.79 - 6.73 (m, 2H),
5.48 (s, 1H), 5.06 (s, 1H), 4.21 (s, 2H), 3.77 (s, 3H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3,
ppm) δ 159.4, 144.4, 135.9, 135.5, 131.2, 129.4, 128.6, 127.4, 119.8, 113.6, 62.2, 55.2, 21.4.
1-fluoro-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3i). White solid (75.4 mg, 82%
yield; 78.1 mg, 85% yield). Mp: 131-132 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10).
1H NMR (400 MHz, CDCl3, ppm) δ 7.80 - 7.74 (m, 2H), 7.21 - 7.16 (m, 2H), 7.12 - 7.05 (m,
2H), 6.80 - 6.74 (m, 2H), 5.50 (s, 1H), 5.10 (s, 1H), 4.25 (s, 2H), 3.78 (s, 3H). 13C 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. HRMS (ESI-TOF) m/z [M +
H]+ calcd. for C16H16FO3S: 307.0799, found 307.0800.
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1-chloro-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3j). White solid (72.6 mg, 75%
yield; 75.5 mg, 78% yield). Mp: 120-121 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10).
1H NMR (400 MHz, CDCl3, ppm) δ 7.67 (d, J = 8.4 Hz, 2H), 7.40 - 7.34 (m, 2H), 7.19 - 7.13
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(m, 2H), 6.79 - 6.73 (m, 2H), 5.50 (s, 1H), 5.11 (s, 1H), 4.24 (s, 2H), 3.78 (s, 3H). 13C 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. HRMS (ESI-TOF) m/z [M + H]+ calcd. for C16H16ClO3S: 323.0503, found
323.0501.
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1-bromo-4-((2-(4-methoxyphenyl)allyl)sulfonyl)benzene (3k). White solid (89.2 mg, 81%
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yield; 93.7 mg, 85% yield). Mp:114-115 C. Eluent: EtOAc/Petroleum ether (V/V = 1:10).
1H NMR (400 MHz, CDCl3, ppm) δ 7.59 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.16
(d, J = 8.8 Hz, 2H), 6.76 (d, J = 8.8 Hz, 2H), 5.51 (s, 1H), 5.12 (s, 1H), 4.24 (s, 2H), 3.80 (s,
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3H). C NMR (100 MHz, CDCl3, ppm) δ 159.7, 137.4, 135.8, 132.1, 130.8, 130.2, 128.9,
127.4, 120.3, 113.8, 62.5, 55.3. HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C16H15BrO3SNa:
388.9817, found 388.9830.
1-bromo-4-(3-((4-methoxyphenyl)sulfonyl)prop-1-en-2-yl)benzene (3l). Yellow oil (91.4 mg,
83% yield; 95.9 mg, 87% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (400
MHz, CDCl3, ppm) δ 7.71 (d, J = 8.8 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 NMR (150 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. HRMS (ESI-TOF)
m/z [M + Na]+ calcd. for C16H15BrO3SNa: 388.9817, found 388.9827.
1-bromo-4-(3-tosylprop-1-en-2-yl)benzene (3m).12a White solid (82.2 mg, 78% yield; 68.2
mg, 89.6% yield). Mp: 130-132 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR
(600 MHz, CDCl3, ppm) δ 7.63 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 7.8
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Hz, 2H), 7.13 (d, J = 8.4 Hz, 2H), 5.57 (s, 1H), 5.22 (s, 1H), 4.20 (s, 2H), 2.41 (s, 3H). C
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NMR (150 MHz, CDCl3, ppm) δ 144.9, 137.7, 135.7, 135.3, 131.4, 129.6, 128.6, 127.9, 122.3,
122.1, 62.0, 21.6.
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1-bromo-4-(3-((4-chlorophenyl)sulfonyl)prop-1-en-2-yl)benzene (3n). Yellow oil (83.6 mg,
75% yield; 91.4 mg, 82% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (600
MHz, CDCl3, ppm) δ 7.69 (d, J = 8.4 Hz, 2H), 7.41 (dd, J = 19.2, 8.4 Hz, 4H), 7.14 (d, J =
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8.4 Hz, 2H), 5.60 (s, 1H), 5.22 (s, 1H), 4.23 (s, 2H). C NMR (150 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. HRMS (ESI-TOF)
m/z [M + Na]+ calcd. for C15H12BrClO2SNa: 392.9302, found 392.9305.
1-bromo-4-(3-((4-fluorophenyl)sulfonyl)prop-1-en-2-yl)benzene (3o). Yellow oil (75.7 mg,
71% yield; 83.1 mg, 78% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H NMR (600
MHz, CDCl3, ppm) δ 7.78 (dd, J = 8.4, 5.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.16 - 7.11 (m,
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8.4 Hz, 4H), 5.60 (s, 1H), 5.22 (s, 1H), 4.23 (s, 2H). C NMR (150 MHz, CDCl3, ppm)
δ165.8 (d, J = 256.9 Hz), 137.5, 135.5, 134.2, 131.6, 131.5 (d, J = 9.6 Hz), 127.8, 122.5,
122.4, 116.3 (d, J = 22.7 Hz), 62.1. HRMS (ESI-TOF) m/z [M + Na]+ calcd. for
C15H12BrFO2SNa: 378.9597, found 378.9590.
1-fluoro-4-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (3p).21g White solid (59.7 mg, 72%
yield; 63.0 mg, 76% yield). Mp: 87-88 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H
NMR (400 MHz, CDCl3, ppm) δ 7.79 (d, J = 7.2 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.46 (t, J
= 7.6 Hz, 2H), 7.27 - 7.23 (m, 2H), 6.93 (t, J = 8.8 Hz, 2H), 5.54 (s, 1H), 5.19 (s, 1H), 4.24
(s, 2H). 13C NMR (100 MHz, CDCl3, ppm) δ 162.5 (d, J = 248.0 Hz), 138.4, 135.5, 134.9 (d,
J = 3.4 Hz), 133.7, 128.9, 128.6, 128.0 (d, J = 8.2 Hz), 121.9, 115.3 (d, J = 21.6 Hz), 62.2.
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78% yield). Mp: 108-110 C. Eluent: EtOAc/Petroleum ether (V/V = 1:10). H NMR (400
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5.55 (s, 1H), 5.20 (s, 1H), 4.24 (s, 2H), 2.43 (s, 3H). C 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-fluoro-4-(3-((4-methoxyphenyl)sulfonyl)prop-1-en-2-yl)benzene (3r). White solid (73.5 mg,
80% yield; 78.1 mg, 85% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:10). Mp: 69-70 oC.
1H NMR (400 MHz, CDCl3, ppm) δ 7.71 (d, J = 8.8 Hz, 2H), 7.28 (dd, J = 8.8, 5.2 Hz, 2H),
6.99 - 6.90 (m, 4H), 5.55 (s, 1H), 5.20 (s, 1H), 4.24 (s, 2H), 3.87 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm) δ 163.7 (d, J = 3.6 Hz), 161.2, 135.8, 135.0 (d, J = 3.3 Hz), 130.7, 129.9, 128.0
(d, J = 8.1 Hz), 121.6, 115.2 (d, J = 21.6 Hz), 114.1, 62.5, 55.6. HRMS (ESI-TOF) m/z [M
+ Na]+ calcd. for C16H15FO3SNa: 329.0618, found 329.0633.
1-methyl-4-(3-(phenylsulfonyl)prop-1-en-2-yl)benzene (3s). White solid (69.4 mg, 85% yield;
71.9 mg, 88% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:15). Mp: 68-69 oC. 1H NMR
(400 MHz, CDCl3, ppm) δ 7.79 (d, J = 7.2 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.44 (t, J = 7.6
Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 5.55 (s, 1H), 5.14 (s, 1H), 4.26 (s,
13
2H), 2.31 (s, 3H). C NMR (100 MHz, CDCl3, ppm) δ 138.4, 137.9, 136.2, 135.8, 133.5,
129.0, 128.8, 128.6, 126.0, 120.9, 62.1, 21.0. HRMS (ESI-TOF) m/z [M + H]+ calcd. for
C16H17O2S: 273.0949; found: 273.0954.
1-methyl-4-((2-(p-tolyl)allyl)sulfonyl)benzene (3t).12a White solid (77.3 mg, 90% yield; 79.9
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mg, 93% yield). Mp: 81-83 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:15). 1H NMR (400
MHz, CDCl3, ppm) δ 7.66 (d, J = 8.0 Hz, 2H), 7.19 (dd, J = 16.0, 8.0 Hz, 4H), 7.05 (d, J =
8.0 Hz, 2H), 5.54 (s, 1H), 5.12 (s, 1H), 4.23 (s, 2H), 2.39 (s, 3H), 2.31 (s, 3H). 13C NMR (100
MHz, CDCl3, ppm) δ 144.4, 137.7, 136.3, 135.8, 135.4, 129.4, 128.9, 128.5, 126.0, 120.7,
62.1, 21.5, 21.0.
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1-fluoro-4-((2-(p-tolyl)allyl)sulfonyl)benzene (3u). White solid (71.4 mg, 82% yield; 74.9 mg,
86% yield). Mp: 83-84 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:15). 1H NMR (400 MHz,
CDCl3, ppm) δ 7.76 (dd, J = 8.8, 5.2 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 7.10 -7.04 (m, 4H),
13
5.56 (s, 1H), 5.16 (s, 1H), 4.26 (s, 2H), 2.31 (s, 3H). C 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. HRMS (ESI-TOF) m/z [M +
Na]+calcd. for C16H15FO2SNa: 313.0669, found 313.0670.
2-(3-(phenylsulfonyl)prop-1-en-2-yl)thiophene (3v). White solid (67.4 mg, 85% yield; 69.8
mg, 88% yield). Mp: 71-73 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:20). 1H NMR (400
MHz, CDCl3, ppm) δ 7.84 (d, J = 7.6 Hz, 2H), 7.58 (t, J = 7.6 Hz, 1H), 7.47 (t, J = 7.6 Hz,
2H), 7.12 (d, J = 5.2 Hz, 1H), 6.91 (d, J = 3.6 Hz, 1H), 6.88 - 6.84 (m, 1H), 5.63 (s, 1H), 5.03
(s, 1H), 4.22 (s, 2H). 13C NMR (100 MHz, CDCl3, ppm) δ 163.8, 142.7, 130.9, 130.4, 129.7,
127.5, 125.2, 119.4, 114.1, 62.6, 55.6. HRMS (ESI-TOF) m/z [M + Na]+ calcd. for
C13H12O2S2Na: 287.0171, found 287.0175.
2-(3-tosylprop-1-en-2-yl)thiophene (3w).12a White solid (75.2 mg, 90% yield; 77.7 mg, 93%
o
1
yield). Mp: 83-84 C. Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (400 MHz,
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CDCl3, ppm) δ 7.70 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 7.6 Hz, 2H), 7.11 (d, J = 5.2 Hz, 1H),
6.91 (d, J = 3.6 Hz, 1H), 6.85 (dd, J = 4.8, 3.6 Hz, 1H), 5.60 (s, 1H), 4.99 (s, 1H), 4.17 (s,
2H), 2.39 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm) δ 144.7, 142.6, 135.2, 130.2, 129.5,
128.7, 127.5, 125.3, 125.2, 119.5, 62.4, 21.6.
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2-(3-((4-methoxyphenyl)sulfonyl)prop-1-en-2-yl)thiophene (3x). White solid (75.6 mg, 92%
yield; 78.0 mg, 95% yield). Mp: 79-80 oC. Eluent: EtOAc/Petroleum ether (V/V = 1:10). 1H
NMR (400 MHz, CDCl3, ppm) δ 7.75 (d, J = 8.8 Hz, 2H), 7.13 (d, J = 5.2 Hz, 1H), 6.89 (m,
4H), 5.62 (s, 1H), 5.01 (s, 1H), 4.19 (s, 2H), 3.85 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm)
δ 163.8, 142.7, 131.0, 130.4, 129.7, 127.6, 125.3, 125.3, 119.5, 114.1, 62.6, 55.7. HRMS
(ESI-TOF) m/z [M + Na]+ calcd. for C14H14O3S2: 317.0277, found 317.0284.
((2-phenylbut-2-en-1-yl)sulfonyl)benzene (5a). Colorless oil (66.2 mg, 81% yield; 69.5 mg,
85% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:20). 1H NMR (400 MHz, CDCl3, ppm)
Z isomer δ 7.75 (d, J = 7.6 Hz, 2H), 7.46 - 7.34 (m, 4H), 7.27 - 7.03 (m, 4H), 6.09 (q, J = 7.2
Hz, 1H), 4.37 (s, 2H), 1.66 (d, J = 7.2 Hz, 3H). E isomer δ 7.75 (d, J = 7.6 Hz, 2H), δ 7.58 -
7.48 (m, 4H), 7.27 - 7.03 (m, 4H), 5.78 (q, J = 7.2 Hz, 1H), 4.13 (s, 2H), 1.63 (d, J = 7.2 Hz,
3H). 13C NMR (100 MHz, CDCl3) δ 140.8, 138.9, 138.9, 137.9, 133.4, 133.3, 133.0, 132.9 ,
128.9, 128.8, 128.6, 128.4, 128.3, 128.2, 128.1, 127.1, 127.1, 126.2, 64.9, 57.3, 15.3, 14.9.
HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C16H16O2SNa: 295.0763, found 295.0758.
1-fluoro-4-((2-phenylbut-2-en-1-yl)sulfonyl)benzene (5b). Colorless oil (66.2 mg, 76% yield;
1
68.8 mg, 79% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (400 MHz,
CDCl3, ppm) Z isomer δ 7.74 - 7.70 (m, 2H), δ 7.25 - 6.99 (m, 7H), 6.11 (q, J = 7.2 Hz, 1H),
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4.38 (s, 2H), 1.74 (d, J = 7.2 Hz, 3H). E isomer δ 7.74 - 7.70 (m, 2H), δ 7.25 - 6.99 (m, 7H),
5.82 (q, J = 7.2 Hz, 1H), 4.14 (s, 2H), 1.66 (d, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ 165.7 (d, J = 256.2 Hz), 140.7, 135.0, 133.2, 133.0, 131.4 (d, J = 9.6 Hz), 131.2 (d, J = 9.6
Hz), 128.9, 128.8, 128.6, 128.3, 128.2, 127.3, 127.2, 126.2, 65.3, 57.5, 15.4, 15.1. HRMS
(ESI-TOF) m/z [M + Na]+calcd. for C16H15FO2SNa : 313.0669, found 313.0680.
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1-chloro-4-((2-phenylbut-2-en-1-yl)sulfonyl)benzene (5c). Colorless oil (64.4 mg, 70% yield;
1
68.1 mg, 74% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (400 MHz,
CDCl3) Z isomer δ 7.63 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 8.8 Hz, 2H), 7.19 (dd, J = 4.8, 1.6
Hz, 3H), 7.10 (dd, J = 6.8, 2.8 Hz, 2H), 6.11 (q, J = 6.8 Hz, 1H), 4.38 (s, 2H), 1.75 (d, J = 6.8
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ140.5, 140.2, 137.3, 133.3, 133.1, 129.9, 129.8, 129.0,
128.7, 128.6, 128.3, 128.1, 127.1, 126.2, 65.2, 57.4, 15.4, 15.1. HRMS (ESI-TOF) m/z [M +
Na]+calcd. for C16H15ClO2SNa: 329.0373, found 329.0382.
The procedure for the synthesis of aliphatic nitrocompounds: The solution of
(nitromethylene)cyclohexane 1h (0.3 mmol) and sodium sulfinates 2 (0.45 mmol) in DMSO
o
(3 mL), was added I2 (10 % mmol), the mixture was stirring at 80 C for 8 h. After the
completion of the reaction, the mixture was poured into water, and extracted by ethyl acetate,
washed with NaCl (aq), dried with anhydrous Na2SO4, then the solvent was removed under
reduced pressure to obtain crude product, further purification by column chromatography on
silica gel gave allyl sulfones.
(R)-((2-(nitromethyl)cyclohex-2-en-1-yl)sulfonyl)benzene (7a). White solid (32.9 mg, 39%
o
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yield). Mp: 77-79 C. Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (500 MHz,
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CDCl3) δ 7.93 - 7.91 (m, 2H), 7.69 (d, J = 7.5 Hz, 1H), 7.60 (t, J = 7.7 Hz, 2H), 6.48 (t, J =
3.5 Hz, 1H), 5.75 (d, J = 14.0 Hz, 1H), 4.97 (d, J = 14.0 Hz, 1H), 4.12 - 4.07 (m, 1H), 2.34 -
2.26 (m, 1H), 2.22 - 2.13 (m, 1H), 2.07 - 1.91 (m, 2H), 1.63-1.73 (m, 1H), 1.61 - 1.57 (m,
1H). 13C NMR (100 MHz, CDCl3) δ 143.6, 138.0, 134.0, 129.4, 128.7, 120.5, 80.5, 60.7, 25.0,
23.5, 15.7. HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C13H15NO4SNa: 304.0614, found
304.0603.
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(R)-1-methyl-4-((2-(nitromethyl)cyclohex-2-en-1-yl)sulfonyl)benzene (7b). White solid (36.3
mg, 41% yield). Mp: 87-89 oC. Eluent: EtOAc/Pet ether (V/V = 1:20). 1H NMR (500 MHz,
CDCl3) δ 7.80 - 7.77 (m, 2H), 7.40 - 7.37 (m, 2H), 6.46 (t, J = 3.5 Hz, 1H), 5.74 (d, J = 14.0
Hz, 1H), 4.96 (d, J = 14.0 Hz, 1H), 4.08 - 4.05 (m, 1H), 2.47 (s, 3H), 2.33 - 2.12 (m, 2H),
2.06 - 1.91 (m, 2H), 1.73 - 1.64 (m, 1H), 1.57 - 1.52 (m, 1H). 13C NMR (100 MHz, CDCl3) δ
145.1, 143.4, 135.0, 123.0, 128.7, 120.7, 80.5, 60.7, 25.0, 23.5, 21.7, 15.8. HRMS (ESI-TOF)
m/z [M + Na]+ calcd. for C14H17NO4SNa: 318.0770, found 318.0762.
(R)-1-methoxy-4-((2-(nitromethyl)cyclohex-2-en-1-yl)sulfonyl)benzene (7c). Colorless oil
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(42.0 mg, 45% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (600 MHz,
CDCl3) δ 7.82 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H), 6.45 (s, 1H), 5.73 (d, J = 13.8 Hz,
1H), 4.95 (d, J = 14.4 Hz, 1H), 4.03 (d, J = 3.0 Hz, 1H), 3.89 (s, 3H), 2.27 (d, J = 19.2 Hz,
1H), 2.20 - 2.12 (m, 1H), 1.95 (d, J = 15.0 Hz, 2H), 1.71 - 1.65 (m, 1H), 1.59 - 1.51 (m, 1H).
13C NMR (150 MHz, CDCl3) δ 164.0, 143.3, 130.8, 129.3, 120.8, 114.5, 80.5, 60.9, 55.7,
25.0, 23.5 15.8. HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C14H17NO5SNa: 334.0720,
found 334.0718.
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(R)-1-bromo-4-((2-(nitromethyl)cyclohex-2-en-1-yl)sulfonyl)benzene (7d). Colorless oil
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(36.7 mg, 34% yield). Eluent: EtOAc/Petroleum ether (V/V = 1:20). H NMR (600 MHz,
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CDCl3) δ 7.76 (dd, J = 21.0, 8.4 Hz, 4H), 6.50 (s, 1H), 5.75 (d, J = 13.8 Hz, 1H), 4.98 (d, J
= 13.8 Hz, 1H), 4.09 (s, 1H), 2.31 (d, J = 19.2 Hz, 1H), 2.23 - 2.15 (m, 1H), 1.98 - 2.02 (m,
1H), 1.90 (dd, J = 15.0, 2.4 Hz, 1H), 1.68-1.74 (m, 1H), 1.60 (s, 1H). 13C NMR (150 MHz,
CDCl3) δ 144.0, 136.9, 132.79, 130.29, 129.59, 120.2, 80.5, 60.7, 24.9, 23.5, 15.7. HRMS
(ESI-TOF) m/z [M + Na]+ calcd. for C13H14BrNO4SNa: 383.9699, found 383.9693.
ASSOCIATED CONTENT
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Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at
DOI: 10.1021/ x0xx00000x. Scanned copies of 1H and 13C NMR spectra of the synthesized
compounds (PDF) Crystallographic data for compound 7a (CCDC 1565191) and 8 (CCDC
1565190) (CIF).
AUTHOR INFORMATION
Corresponding Author
*,† E-mail: yfchen@wit.edu.cn
*,‡ E-mail: xmshi@usf.edu
ACKNOWLEDGMENTS
We are grateful to the National Natural Science Foundation of China (21002076) and the
Graduate Education Innovation Fund of Wuhan Institute of Technology (CX2016167). We
also thank the NSF (CHE-1665122) and NSFC (21629201) for financial support.
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For selected examples of other metal complexes or acid catalyzed the allylic
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18 Proposed mechanism involved a sequential sulfonyl radical addition:
ArO2S
Ph
Ph
ArO2S
Ph
ArSO2
SO2Ar
SO2Ar
Ph
NO2
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