I2-DMSO-H2O: A Metal-Free Combination System for the Oxidative Addition of Alkynes to Access (E)-α-Iodo-β-methylsulfonylalkenes

Article abstract of DOI:10.1021/acs.joc.9b02302

A simple and green reaction was discovered for iodization-methylsulfoxidation of alkynes to access (E)-α-iodo-β-methylsulfonylalkenes. This is the first report for the synthesis of iodovinyl methylsulfones by employing alkynes to react with molecular iodi

Full text of DOI:10.1021/acs.joc.9b02302

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Note
I2-DMSO-H2O: A Metal Free Combination System for the Oxidative
Addition of Alkynes to Access (E)-#-Iodo-#-methylsulfonylalkenes
Peng Zhou, Yupeng Pan, Hua Tan, and Weibing Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b02302 • Publication Date (Web): 30 Oct 2019
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I2-DMSO-H2O: A Metal Free Combination System for the Oxidative
Addition of Alkynes to Access (E)-α-Iodo-β-methylsulfonylalkenes
Peng Zhou†, Yupeng Pan*,‡, Hua Tan† and Weibing Liu*,†
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†
College of Chemistry, Guangdong University of Petrochemical Technology, 2 Guandu Road, Maoming 525000,
‡
P. R. China; Email address: lwb409@gdupt.edu.cn; Shenzhen Grubbs Institute, Southern University of Science
and Technology (SUSTech), Shenzhen, 518055, P. R. China; Email address:panyp@mail.sustc.edu.cn.
O
S
O
S
I
I2 / H2O
R
+
O
R
Metal free and high efficient
Wide substrate scope
H2O as the source of "O"
Abstract: A simple and green reaction was discovered for iodization-methylsulfoxidation of
alkynes to access (E)-α-iodo-β-methylsulfonylalkenes. This is the first report for synthesis of
iodovinyl methylsulfones by employing alkynes to react with molecular iodine (I2), dimethyl
sulfoxide (DMSO) and H2O. Additionally, this protocol represents a new avenue for utilizing
DMSO as the source of the –SO2Me group and H2O as the “O” source for the construction of
–SO2Me group from DMSO, which is a valuable finding.
Direct adjacent difunctionalization of alkynes is considered to be one of the most powerful
methods to install two functional groups efficiently, in one step, onto a C-C triple bond. The reaction
has evolved as one of the most straightforward approaches to synthesize structurally diverse and
complex chemicals from simple starting materials.1 To date, this methodology has been widely used to
synthesize halovinyl sulfides from alkynes.2 Halovinyl sulfides are a valuable and important class of
compounds in organic synthesis, and have attracted particular interest3 for their potentially applications
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as starting materials or synthetic intermediates for synthesis of naturally occurring molecules, organic
materials, bioactive compounds, pharmaceuticals and industrial chemicals. Thus far, many successful
methods have been developed to access halovinyl sulfides, such as β-haloalkenylsulfones and
chloroalkenylthioethers, from alkynes.4 However, the reports for synthesis of iodovinylsulfones
directly from the reaction of alkynes with molecular iodine (I2) and dimethyl sulfoxide (DMSO) are
very vare so far. Iodovinylsulfones, as versatile alkenylic intermediates with both a sulfonyl- and an
iodine-bearing functionality, can be efficiently utilized for selective synthesis of alkenylsulfones,
iodides and many other polysubstituted alkenes by the further transformations of the iodo and sulfonyl
moieties. In recent decades, the utilization of DMSO has flourished, as DMSO is not only an effective
high-boiling polar solvent5 and a gentle oxidant,6 but also frequently employed as a source of –C1,7
–O,8 –SMe,9 –SOMe10 and –CH2SOMe11 for organic transformations, being directly inserted into the
target molecules.
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Figure 1. X-ray structure of 1-fluoro-4-((E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (2k).
In this context, and in line with our current research interests,12 herein we report an unprecedented
reaction, which could access methylsulfones by employing DMSO as the –SO2Me source (Scheme 1).
The structure of the product 2 has been confirmed by 1H NMR, 13C NMR {1H} , and HR-MS, and its
configuration was further verified by NMR-NOE13 and X-ray (Figure 1). However, in a sharp contrast,
the reports for utilization of DMSO as a source of –SO2Me are extremely rare so far.14
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Scheme 1. Synthesis of iodovinylmethylsulfones.
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O
S
O
S
I
I2
R
+
+
H2O
120 °C
O
R
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At the outset of our studies, phenylacetylene 1a was employed as a model substrate to react with
I2 in DMSO and H2O to identify the optimal reaction conditions, the results are rendered in Table 1.
We are pleased to find that this reaction proceeded expeditiously at 120 °C. After screening the
reaction time, we found that 25 minutes was enough for completing the reaction and resulted the
expected product 1-(E)-1-iodo-2-(methylsulfinyl)vinyl)benzene 2a in 80% yield (Table 1, entries 1-4).
No significant improvement in yield was obtained when elevating the reaction temperature to 140 °C
(Table 1, entry 5). However, a steep decline in yield was observed when the reaction temperature was
lowered to 100 °C (Table 1, entry 6). The reaction could not proceed at all when it was conducted at 70
°C or at room temperature (Table 1, entries 7-8). Subsequently, the effect of I2 loading was investigated:
we found no enhancement in the yield of 2a when increasing the I2 loading to 1.5 equiv. or decreasing
it to 0.6 equiv. (Table 1, entries 9-10).
Table 1. Optimization studies a
O
S
O
S
I
I2
Ph
+
H2O
+
O
Ph
1a
2a
Entry
Iodine(1.0 equiv.)
Temperature
120 °C
120 °C
120 °C
120 °C
140 °C
100°C
Time (m)
10
Yield%b
32
1
2
I2
I2
I2
I2
I2
I2
I2
I2
I2
I2
20
73
3
25
80
4
30
80
5
25
80
6
25
57
7
70 °C
25
--
8
R.T.
25
--
9c
10d
120 °C
120 °C
25
80
25
80
a Reaction conditions: 1a (0.25 mmol), I2 (1.0 equiv.), DMSO (1.0 mL), H2O (0.5 mL); b GC yield; c I2:
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0.6 equiv.; d I2: 1.5 equiv..
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Based on the results of the above optimization study (Table 1), we decided to carry out all of the
following reactions with 0.6 equiv of I2 in DMSO at 120 °C for 25 minutes unless otherwise specified
(Scheme 2). We first tested a series of different terminal alkynes to evaluate the efficiency and the
substrate scope of this iodization-methylsulfoxidation to access the desired iodovinyl methylsulfones.
To our satisfaction, despite the varying electronic natures of the different functional groups and
substitution patterns on the phenyl ring, all of the tested terminal arynes were tolerated for this
conversion and all afforded the desired products in moderate yields (Scheme 2, 62%-81%). As shown
in Scheme 2, we noticed that the influence of the different functional groups and substitution patterns
on this transformation was unpredictable. For instance, the electro-donating groups (3-Me, 4-Me, 4-Et,
4-nPr, 4-CH2CN and 4-tBu) on the phenyl ring gave the required products in 67%-81% yield, whereas
those bearing electro-withdrawing groups (2-Cl, 3-Cl, 4-Cl, 2-F, 3-F, 4-F and 4-CF3) afforded the
expected product with 62%-76% yields. Additionally, the outcome of the yield for this conversion
appeared to be almost unaffected by the location of the same substituent at different positions of the
phenyl ring. For example, when phenylacetylene was substituted by –Cl or –F at the ortho, meta or
para position, the corresponding positional isomers were afforded with almost identical yields. For this
reaction, it is puzzling that both the strong electro-withdrawing group –CF3 and the strong
electro-donating group –OCH3 on the phenyl ring of phenylacetylene were unfavorable. In the former
case, the substrate 1-ethynyl-4-(trifluoromethyl)benzene led to the expected product
1-(trifluoromethyl)-4-(E)-1-iodo-2-(methylsulfinyl)vinyl)benzene with only 62% yield. In the latter
case, the substrates 4-methoxyphenylacetylene and 3,4-dimethoxyphenylacetylene failed to give their
desired product.
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Scheme 2. Scope of the substrates (all the reactions were carried out on 1 0.5 mmol scale, I2 0.6
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equivalent, DMSO 1.0 mL, H2O 0.5 mL. Isolated yield is given in the Scheme.).
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9
O
S
O
S
I
I2 (0.6 equiv.)
+
H2O
R
+
120 °C, 25-60 m
O
2
R
1
I
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I
I
I
O S O
O S O
2a 72%
O S O
O S O
2b 75%
Et
2d 72%
2c 70%
I
I
I
I
O S O
O S O
O S O
O S O
But
Cl
I
n-Pr
2h 70%
CN 2g 81%
2f 73%
2e 67%
F
I
I
I
Cl
I
F
Cl
O S O
O S O
2k 74%
O S O
2l 76%
O S O
O S O
F
2m 76%
2j 72%
2i 75%
O
I
I
I
I
S O
Ph
S O
O
O S O
S O
O
S O
O
F3C
I
2r 53%
2q 70%
2p 71%
2n 62%
2o 69%
Next, several terminal alkyl alkynes were evaluated under the optimal conditions. We found that
although all the tested substrates were compatible for this protocol, the reactivity of these compounds
was slightly poorer than for the tested terminal arynes. In general, all these terminal alkyl alkynes led to
their corresponding product with acceptable yield when the reaction time was prolonged to 60 m. To
further expand the substrate scope, internal alkynes, such as oct-4-yne, hept-3-yne and
1-(prop-1-ynyl)benzene, were employed to conduct this conversion. These internal alkynes proved to
be reluctant substrates for this transformation: the symmetrical internal alkyne oct-4-yne resulted in the
expected product (E)-4-iodo-5-(methylsulfinyl)oct-4-ene with only 53% yield (Scheme 2, 2r) and the
unsymmetric substrates furnished a complex reaction system. Finally, it is worth noting that the liquid
iodovinyl methylsulfones (2o-2r) are volatile compounds when pure.
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For the application of the products, a synthetic transformation of 2k was conducted, as showed in
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Scheme
3.
A
simple
workup
afforded
in
the
derived
product
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1-(4-fluorophenyl)-2-(methylsulfonyl)ethanone with 75% yield.
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Scheme 3. Transformation of 1-fluoro-4-((E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (2k) to
1-(4-fluorophenyl)-2-(methylsulfonyl)ethanone.
O
I
NaOAc (2.0 eq), 90 °C
DMSO/H2O = 9:1, 5 h
O S O
75%
O S O
F
F
To shed some light on the mechanism of this iodization-methylsulfoxidation, several control
experiments were conducted (Scheme 4). Firstly, no obvious influence on the product formation was
noticed when the reaction was performed under oxygen or nitrogen atmosphere (Scheme 4, eq 1 and eq
2), which rules out the possibility of the involvement of atmospheric oxygen for the formation of
–SO2Me group. However, this transformation does not occur at all when the reaction was conducted
under nitrogen atmospheres in glove box with anhydrous DMSO, thereby confirming that one oxygen
atom of the –SO2Me group in the product is derived from the H2O in DMSO (Scheme 4, eq 3). As
expected, radical inhibition with excess 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) entirely
quenched this conversion (Scheme 4, eq 4), suggesting a radical mechanism was likely to be involved
for this transformation. To gain further insight into the mechanism, when the reaction of 1a was
conducted in the presence of 0.5 mL of H218O, the 18O-labeled product 2s was obtained in 72% yield
(Scheme 4, eq 5), which completely confirmed the fact that one oxygen atom of the –SO2Me group in
the product is derived from H2O.
Scheme 4. Control experiments.
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given conditions
N2
given conditions
(2)
2a
+
+
DMSO
2a
1a +
DMSO
H2O
H2O
(1)
1a
+
O2
80%
80%
given conditions
given conditions
N2
anhydrous glove box
+
+
DMSO
1a
H2O
(4)
+
1a
2a
2a
DMSO
(3)
TEMPO
(5)
0%
0%
18O
I
given conditions
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1a
H
18O
+
+
S
DMSO
2
O
Ph
2s 72%
0.5 mL
Scheme 5. Proposed mechanism.
O
O
I
O
S
Ph
S
OI
Ph
I
S
DMSO
OMe
1a
I2
I
I
DMSO
S
I
H
H
I2
D
A
B
C
S
1a
I2
IO
O
I
O
I
O
S
I
I
Ph
I
S
Ph
I
S
Ph
I
S
OH
H
Ph
H2O
O
H
H
I
H
E
2a
F
G
The mechanism for this conversion is unclear. However, according to the above control
experiments and the existing related literature, a possible mechanism is illustrated in Scheme 5,
exemplified by the formation of 2a. Initially, I2 reacted with DMSO at high temperature to afford an
iodinated sulphide A, by a similar process was reported by Braga’s group.15 At high temperature, A
quickly decomposed and converted to a sulfinyl iodide cation B. The subsequent addition of A to the
carbon-carbon triple bond of phenylacetylene (1a) resulted in the adduct iodovinylsulfoxidecation C
via the mechanism proposed by Wang’s group.16 The subsequently abstraction of a methyl group from
C by the weakly nucleo-philic DMSO to afford iodovinylsulfoxide species D.11 In the next step,
iodovinylsulfoxide species D underwent a similar process as from DMSO to B (Scheme 5) in the
presence of I2 to furnish another iodovinylsulfoxidecation F, which would be quickly converted to
another intermediate G by the nucleophilic attack of H2O. Finally, the elimilation of HI from G
produces the desired product 2a.
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In conclusion, we have disclosed
a
simple synthetic route to achieve
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(E)-α-iodo-β-methylsulfonylalkenes, which is the first example for synthesis of iodovinyl
methylsulfones via an iodization-methylsulfoxidation of alkynes with I2 and DMSO. In this reaction,
DMSO is an efficient reagent for methylsulfoxidation of alkynes at high temperature. Additionally, this
protocol is a simple yet powerful method for the construction of iodovinyl methylsulfones with a broad
substrate scope and excellent regio-selectivity. The presented organic transformation represents a new
avenue for utilizing DMSO as a source of the methylsulfonyl group. Further studies on the mechanism
and applications are in progress in our laboratory, and we expect many novel methodologies employing
DMSO as –SOMe and –SO2Me sources to arise in the near future.
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EXPERIMENTAL SECTION
General Information. All the reactions were carried out at 120 °C (oil bath) for 25-60 m in a
round-bottom flask equipped with a magnetic stir bar. Unless otherwise stated, all reagents and
1
solvents were purchased from commercial suppliers and used without further purification. H NMR
and 13C NMR {1H} spectra were recorded on a 400MHz spectrometer in solutions of CDCl3 using
tetramethyl silane as the internal standard; δ values are given in ppm, and coupling constants (J) in Hz.
HR-MS were obtained on a Q-TOF micro spectrometer.
Typical procedure: 1-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2a).
A mixture of phenylacetylene (1a) (52 mg, 0.5 mmol), I2 (76 mg, 0.3 mmol), DMSO (1.0 mL) and H2O
(0.5 mL) was added successively in a round-bottom flask, and the resulting solution was stirred for 25
m at 120°C (oil bath). The mixture was purified by column chromatography on silica gel to afford
product 2a with PE/EA = 10/1 as the eluent.
Typical procedure: a larger scale experiment to synthesize 2k
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A mixture of 1-ethynyl-4-fluorobenzene (1k) (1.20 g, 10 mmol), I2 (1.52 g, 6 mmol), DMSO (8.0 mL)
and H2O (0.5 mL) was added successively in a round-bottom flask, and the resulting solution was
stirred for 45 m at 120°C (oil bath). The mixture was purified by column chromatography on silica gel
with PE/EA = 10/1 as the eluent to afford the desired product 2k with 69% yield (2.24 g).
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1-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2a)
I
O S O
1
Yield: 72% (110 mg); a colorless solid; m.p. 99–101 °C; H NMR (CDCl3, 400 Hz) δ 7.46 (m, 2H),
7.41 (m, 3H), 7.31 (s, 1H), 2.67 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 140.3, 139.4, 130.4, 128.3,
127.8, 114.9, 43.0; HRMS (ESI): calcd for C9H9INaO2S: [M+Na+] 330.9260, found 330.9265.
1-(E)-1-iodo-2-(methylsulfonyl)vinyl)-3-methylbenzene (Scheme 2, 2b)
I
O S O
1
Yield: 75% (120 mg); a colorless solid; m.p. 105–107 °C; H NMR (CDCl3, 400 Hz) δ 7.29 (s, 1H),
7.28 (br, 3H),7.19 (m, 1H), 2.67 (s, 3H), 2.39 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 140.1, 139.3,
138.2, 131.2, 128.3, 128.2, 124.9, 115.2, 43.5, 21.3; HRMS (ESI): calcd for C10H11INaO2S: [M+Na+]
344.9416, found 344.9422.
1-(E)-1-iodo-2-(methylsulfonyl)vinyl)-4-methylbenzene (Scheme 2, 2c)17
I
O S O
Yield: 70% (112 mg); a colorless solid; m.p. 108–110 °C; 1H NMR (CDCl3, 400 Hz) δ 7.38 (d, J = 8.4
Hz, 2H), 7.28 (s, 1H), 7.20 (d, J = 8.4 Hz, 2H), 2.67 (s, 3H), 2.37 (s, 3H); 13C NMR {1H} (CDCl3, 100
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Hz) δ 140.9, 139.8, 136.5, 129.0, 128.0, 115.5, 43.0, 21.4; HRMS (ESI): calcd for C10H11INaO2S:
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6
7
[M+Na+] 344.9416, found 344.9418.
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1-ethyl-4-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2d)
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I
O S O
Yield: 72% (120 mg); a colorless solid; m.p. 114–116 °C; 1H NMR (CDCl3, 400 Hz) δ 7.41 (d, J = 8.4
Hz, 2H), 7.28 (s, 1H), 7.22 (d, J = 8.4 Hz, 2H), 2.68 (q, J = 7.6 Hz, 2H), 2.66 (s, 3H), 1.25 (t, J = 7.6
Hz, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 147.1, 139.9, 136.7, 128.1, 127.8, 115.5, 42.9, 28.7, 15.0;
HRMS (ESI): calcd for C11H13INaO2S: [M+Na+] 358.9573, found 358.9565.
1-(E)-1-iodo-2-(methylsulfonyl)vinyl)-4-propylbenzene (Scheme 2, 2e)
I
O S O
Yield: 67% (117 mg); a colorless solid; m.p. 123–124 °C; 1H NMR (CDCl3, 400 Hz) δ 7.40 (d, J = 8.4
Hz, 2H),7.28 (s, 1H), 7.20 (d, J = 8.4 Hz, 2H),2.64 (s, 3H), 2.60(q, J = 7.6 Hz, 2H), 1.64 (m, 2H), 0.95
(t, J = 7.6 Hz, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 145.7, 139.9, 136.7, 128.4, 128.0, 115.4, 42.9,
37.8, 24.1, 13.8; HRMS (ESI): calcd for C12H15INaO2S: [M+Na+] 372.9729, found 372.9740.
1-tert-butyl-4-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2f)
I
O S O
1
Yield: 73% (132 mg); a colorless solid; m.p. 102–104 °C; H NMR (CDCl3, 400 Hz) δ 7.42 (m, 4H),
7.29 (s, 1H), 2.64 (s, 3H), 1.33 (s, 9H); 13C NMR {1H} (CDCl3, 100 Hz) δ 154.0, 139.9, 136.3, 127.9,
125.3, 115.4, 42.9, 34.9, 31.1; HRMS (ESI): calcd for C13H18IO2S: [M+H+] 365.0066, found 365.0074.
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2-(4-(E)-1-iodo-2-(methylsulfonyl)vinyl)phenyl)acetonitrile (Scheme 2, 2g)
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I
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9
NC
O S O
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Yield: 81% (1140 mg); a pale yellow solid; m.p. 108–110 °C; 1H NMR (CDCl3, 400 Hz) δ 7.48 (d, J =
8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.33 (s, 1H), 3.79 (s, 2H), 2.76 (s, 3H); 13C NMR {1H} (CDCl3,
100 Hz) δ 140.2, 139.4, 132.1, 128.6, 127.8, 43.2, 29.6, 23.5; HRMS (ESI): calcd for C11H10INNaO2S:
[M+Na+] 369.9369, found 369.9371.
1-chloro-4-((Z)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2h)
I
O S O
Cl
1
Yield: 70% (119 mg); a colorless solid; m.p. 116–117 °C; H NMR (CDCl3, 400 Hz) δ 7.38 (m, 4H),
7.31 (s, 1H), 2.75 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 140.3, 137.7, 136.5, 129.3, 128.6, 113.4,
43.1; HRMS (ESI): calcd for C9H9ClIO2S: [M+H+] 342.9051, found 342.9067.
1-chloro-3-((Z)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2i)
I
Cl
O S O
1
Yield: 75% (127 mg); a colorless solid; m.p. 100–102 °C; H NMR (CDCl3, 400 Hz) δ 7.41 (s, 1H),
7.35 (br, 3H), 7.32 (s, 1H), 2.76 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 140.9, 140.6, 134.2, 130.4,
129.5, 127.7, 125.9, 112.6, 43.2; HRMS (ESI): calcd for C9H9ClIO2S: [M+H+] 342.9051, found
342.9071.
1-chloro-2-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2j)
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Cl
I
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7
O S O
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9
Yield: 72% (119mg); a colorless solid; m.p. 91–93 °C; 1H NMR (CDCl3, 400 Hz) δ 7.42 (m, 1H), 7.36
(s, 1H), 7.32 (m, 3H), 2.80 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 141.2, 137.7, 130.9, 130.3,
129.9, 128.8, 126.8, 110.9, 42.7; HRMS (ESI): calcd for C9H9ClIO2S: [M+H+] 342.9051, found
342.9066.
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1-fluoro-4-((Z)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2k)
I
O S O
F
1
Yield: 74% (120 mg); a colorless solid; m.p. 112–114 °C; H NMR (CDCl3, 400 Hz) δ 7.47 (m, 2H),
1
7.31 (s, 1H), 7.08 (m, 2H), 2.73 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ161.6 (d, JC-F = 251.0
4
3
2
Hz),140.2, 135.4 (d, JC-F = 3.5 Hz), 130.2 (d, JC-F = 8.7 Hz), 115.5 (d, JC-F = 22.0 Hz), 113.7, 43.1;
HRMS (ESI): calcd for C9H9FIO2S: [M+H+] 326.9346, found 326.9349.
1-fluoro-3-((Z)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2l)
I
F
O S O
1
Yield: 76% (123 mg); a colorless solid; m.p. 103–105 °C; H NMR (CDCl3, 400 Hz) δ 7.38 (m, 1H),
7.32 (s, 1H), 7.23 (m, 1H), 7.14 (m, 1H), 7.08 (m, 1H), 2.75 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz)
δ 163.0 (d, 1JC-F = 245.0 Hz), 145.1 (d, 4JC-F = 6.7 Hz), 140.6, 130.0 (d, 3JC-F = 8.0 Hz), 123.5 (d, 3JC-F
2
2
= 8.0 Hz), 117.4 (d, JC-F = 21.0 Hz), 112.6 (d, JC-F = 21.9 Hz), 43.2; HRMS (ESI): calcd for
C9H9FIO2S: [M+H+] 326.9346, found 326.9370.
1-fluoro-2-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2m)
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F
I
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6
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O S O
8
9
Yield: 76% (124 mg); a colorless solid; m.p. 97–99 °C; 1H NMR (CDCl3, 400 Hz) δ 7.40 (s, 1H), 7.35
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1
(m, 2H),7.20 (m, 1H), 7.09 (m, 1H) 2.84 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 158.5 (d, JC-F
=
248.0 Hz), 141.4, 132.0 (d, 3JC-F = 8.3 Hz), 129.5 (d, 4JC-F = 3.2 Hz), 127.3 (d, 2JC-F = 21.9 Hz), 124.1
(d, 3JC-F = 3.6 Hz), 115.8 (d, 2JC-F = 20.8 Hz), 106.7, 42.7; HRMS (ESI): calcd for C9H9FIO2S: [M+H+]
326.9346, found 326.9362.
1-(trifluoromethyl)-4-((Z)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 2, 2n)
I
O S O
F3C
Yield: 62% (117 mg); a colorless solid; m.p. 113–114 °C; 1H NMR (CDCl3, 400 Hz) δ 7.66 (d, J = 7.6
Hz, 2H), 7.55 (d, J = 7.6 Hz, 2H),7.37 (s, 1H), 2.79 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 142.8,
1
140.7, 131.1, 128.1, 126.9 (q, JC-F = 269.5 Hz), 125.3, 112.6, 43.3; HRMS (ESI): calcd for
C10H9F3IO2S: [M+H+] 376.9314, found 376.9321.
(E)-2-iodo-1-(methylsulfonyl)hex-1-ene (Scheme 2, 2o)
I
S O
O
Yield: 69% (99 mg); a colorless oil; 1H NMR (CDCl3, 400 Hz) δ 6.54 (s, 1H), 2.45 (t, J = 7.6 Hz, 2H),
2.30 (s, 3H), 1.48 (m, 2H), 1.36 (m, 2H), 0.92 (t, J = 7.6 Hz, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ
133.2, 96.9, 39.5, 30.8, 21.4, 17.4, 13.9; HRMS (ESI): calcd for C7H14IO2S: [M+H+] 288.9753, found
288.9750.
(E)-2-iodo-1-(methylsulfonyl)hept-1-ene (Scheme 2, 2p)
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Yield: 71% (106mg); a colorless oil;1H NMR (CDCl3, 400 Hz) δ 6.54 (s, 1H), 2.43 (t, J = 7.6 Hz, 2H),
2.31 (s, 3H), 1.50 (m, 2H), 1.33 (m, 4H), 0.91 (t, J = 7.6 Hz, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ
133.2, 97.0, 39.7, 30.4, 28.3, 22.4, 17.4, 13.9; HRMS (ESI): calcd for C8H16IO2S: [M+H+] 302.9910,
found 302.9914.
1-(E)-4-iodo-5-(methylsulfonyl)pent-4-enyl)benzene (Scheme 2, 2q)
I
Ph
S O
O
Yield: 70% (123 mg); a pale yellow oil; 1H NMR (CDCl3, 400 Hz) δ 7.29 (t, J = 7.6 Hz, 2H), 7.21 (m,
3H), 7.06 (s, 1H), 3.08 (t, J = 7.6 Hz, 2H), 2.91 (s, 3H), 2.70 (t, J = 7.6 Hz, 2H), 1.96 (m, 2H); 13C
NMR {1H} (CDCl3, 100 Hz) δ 141.0, 138.0, 128.45, 128.41, 126.5, 126.1, 43.6, 39.6, 34.5, 31.7;
HRMS (ESI): calcd for C12H16IO2S: [M+H+] 350.9910, found 350.9928.
(E)-4-iodo-5-(methylsulfonyl)oct-4-ene (Scheme 2, 2r)
O
S O
I
Yield: 53% (84 mg); a colorless oil; 1H NMR (CDCl3, 400 Hz) δ 2.85 (t, J = 7.6 Hz, 2H), 2.52 (t, J =
7.6 Hz, 2H), 2.22 (s, 3H), 1.57 (m, 4H), 0.97 (t, J = 7.6 Hz, 3H), 0.92 (t, J = 7.6 Hz, 3H); 13C NMR
{1H} (CDCl3, 100 Hz) δ 137.2, 106.7, 44.7, 42.5, 22.5, 21.2, 16.6, 13.5, 12.8; HRMS (ESI): calcd for
C9H18IO2S: [M+H+] 317.0066, found 317.0061.
1-(4-fluorophenyl)-2-(methylsulfonyl)ethanone (Scheme 3) 18
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O
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O S O
F
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A colorless solid; 1H NMR (CDCl3, 400 Hz) δ 8.06 (m, 2H), 7.22 (m, 2H), 4.57 (s, 2H), 3.15 (s, 3H).
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1-(E)-1-iodo-2-(methylsulfonyl)vinyl)benzene (Scheme 4, eq 5, 2s)
I
O S O18
1
Yield: 72% (110 mg); a colorless solid; m.p. 99–101 °C; H NMR (CDCl3, 400 Hz) δ 7.46 (m, 2H),
7.40 (m, 3H), 7.31 (s, 1H), 2.66 (s, 3H); 13C NMR {1H} (CDCl3, 100 Hz) δ 140.2, 139.4, 130.4, 128.3,
127.8, 114.9, 43.0; HRMS (ESI): calcd for C9H9IO18OS: [M+H+] 310.9483, found 310.9494.
Supporting Information Available: Copies of 1H and 13C NMR {1H} of all the new compounds. This
material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: lwb409@gdupt.edu.cn; panyp@mail.sustc.edu.cn
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21502066), the
Foundation of Department of Science and Technology of Guangdong Provincial (No.
2016A020221038) and Guangdong Natural Science Foundation (No. 2017A030307006)
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