Silver-promoted decarboxylative sulfonylation of aromatic carboxylic acids with sodium sulfinates

Article abstract of DOI:10.1021/acs.joc.9b01333

A novel and efficient synthesis of sulfones was developed via a silver-promoted decarboxylative sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates for the first time. The approach features operational simplicity and good functional group compatibility and uses readily available starting materials. Furthermore, mechanistic studies reveal that the decarboxylative sulfonylation reaction is likely to proceed via a radical mechanism.

Full text of DOI:10.1021/acs.joc.9b01333

Subscriber access provided by Nottingham Trent University
Note
Silver-Promoted Decarboxylative Sulfonylation of
Aromatic Carboxylic Acids with Sodium Sulfinates
Yongqi Yu, Qianlong Wu, Da Liu, Lin Yu, Ze Tan, and Gangguo Zhu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01333 • Publication Date (Web): 13 Aug 2019
Downloaded from pubs.acs.org on August 13, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
Silver-Promoted Decarboxylative Sulfonylation of Aromatic Carboxylic Acids with Sodium
Sulfinates
7
8
9
Yongqi Yu,† Qianlong Wu,† Da Liu,† Lin Yu,† Ze Tan,†,* and Gangguo Zhu‡
†State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and
Chemical Engineering, Hunan University, Changsha 410082, P. R. China
‡Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, China
ztanze@gmail.com
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
A novel and efficient synthesis of sulfones was developed via silver-promoted decarboxylative
sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates for the first time.
The approach features operational simplicity, good functional group compatibility as well as using
readily available starting materials. Furthermore, mechanistic studies reveal that the
decarboxylative sulfonylation reaction is likely to proceed via a radical mechanism.
Sulfones are a highly valuable class of organic molecules because of their unique bioactivity
and chemical properties.1 They are widely present in various functional materials and
pharmaceutical molecules (Figure 1).2 Moreover, these compounds are also important
intermediates in organic transformations such as Smiles rearrangement3 and Julia olefination.4
Due to their importance, chemists have developed numerous methods for the synthesis of
sulfones.5 Conventionally, they are prepared by the oxidation of sulfides,6 the sulfonylation of
arenes with sulfonyl halides or their derivatives,7 or transition metal-catalyzed cross-coupling
reactions between sulfinic acid salts and aryl halides.8 Recently, approaches based on the insertion
of sulfur dioxide for the synthesis of sulfones have also been reported.9 Despite their usefulness,
these methods tend to suffer from drawbacks such as the use of foul-smelling sulfides, harsh
reaction conditions, requiring prefunctionalized starting materials or the generation of massive
amount of useless by-products. As a consequence, developing efficient and straightforward
strategies for the synthesis of sulfones from readily available starting materials is highly desirable.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 23
1
2
3
4
5
6
7
Figure 1. Biologically active aryl sulfones.
8
9
Over the past several years, decarboxylative cross-coupling of aromatic carboxylic acids has
emerged as a powerful tool in organic synthesis10 since various aryl carboxylic acids are
inexpensive, readily available, chemically nontoxic and easy to store and handle. Early reports by
the groups of Gooßen,11 Su,12 Myers,13 and others14 have shown that benzoic acid derivatives
could undergo decarboxylative couplings to construct new C–C and C–X (X=S, O, N, etc.) bonds.
It is commonly believed that aryl-metal intermediates are generated in situ by loss of CO2 from
metal carboxylates. The resultant aryl organometallic species subsequently can be subjected to
further functionalizations to give various coupling products. In these cases, either Pd/Cu or Pd/Ag
bimetallic catalytic systems are often used for the decarboxylative couplings.15 Furthermore,
copper-only systems for decarboxylative couplings have also been reported recently.14b,16 In
contrast, silver-catalyzed or promoted decarboxylative coupling of aromatic carboxylic acids has
been less explored and only a few reports have been documented so far.12b,17 In 2012, Greaney
reported a silver-catalyzed intramolecular decarboxylative arylation reaction of benzoic acids to
form fluorenones.17a In 2015, Su reported the synthesis of biaryl compounds via an intermolecular
Minisci reaction of aromatic carboxylic acids with (hetero)arenes catalyzed by a Ag2SO4/K2S2O8
system.12b Later on, Natarajan reported a Ag2CO3-promoted ipso-nitration reaction of aromatic
and aliphatic carboxylic acids by employing NO2BF4 as the nitrating agent.17b Driven by our
interest in decarboxylative cross-couplings,18 we launched a research towards the synthesis of
sulfones. A closer survey of literature reveals that decarboxylative sulfonylation of cinnamic acids
and propiolic acids has been reported by several groups,19 however, decarboxylative sulfonylation
of aromatic carboxylic acids remains unprecedented. Herein, we report the first example of
silver-promoted decarboxylative sulfonylation reaction of aromatic carboxylic acids with sodium
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
sulfinates.
Table 1. Optimization of the Reaction Conditionsa
ACS Paragon Plus Environment

Page 3 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
aUnless otherwise noted, the reactions were performed using 1a (0.3 mmol), 2a (2.0 equiv), Ag
salt (1.0 equiv), ligand (40 mol %) and Na2CO3 (2.0 equiv) in a solvent (3.0 mL) at 160 oC for 18
b
c
h under O2 in sealed tubes. Isolated yield. NR = no reaction. ND = not detected. CuCl2 (0.06
mmol) was added. dWithout Na2CO3. eUnder N2 atmosphere. fUnder air atmosphere. gK2S2O8 (0.6
mmol) was added.
Our investigation commenced by choosing 2-nitrobenzoic acid (1a) and sodium
4-methylbenzenesulfinate (2a) as the model substrates. When the reaction mixture of 1a (0.3
mmol), 2a (0.6 mmol), CuCl2 (0.06 mmol), Ag2CO3 (0.3 mmol), 1,10-phenanthroline (0.12 mmol)
and Na2CO3 (0.6 mmol) in toluene (3.0 mL) was stirred at 160 oC under O2 for 18 h, 51% yield of
the desired decarboxylative sulfonylation product 3aa was isolated (Table 1, entry 1). To our
surprise, when the model reaction was performed in the absence of CuCl2, the desired product 3aa
could be isolated in 57% yield (Table 1, entry 2). Several commonly used silver salts such as
AgNO3, AgOAc and Ag2O were subsequently explored, however no further improvement was
observed (Table 1, entries 3–5). Control experiments showed that silver salt is essential for the
transformation to proceed (Table 1, entry 6). The use of 2,2′-bipyridine in place of
1,10-phenanthroline resulted in lower yield (Table 1, entry 7). It should be noted that no desired
product was detected when the model reaction was carried out with triphenylphosphine as the
ligand or in the absence of the ligand (Table 1, entries 8, 9). Interestingly, an even better result was
obtained when the reaction was performed in the absence of Na2CO3 (Table 1, entry 10). When the
reaction was carried out under N2 atmosphere, a comparable yield was obtained (Table 1, entry 10
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 23
1
2
3
4
5
6
7
8
9
vs. entry 11), suggesting that O2 is not essential for the reaction. It was observed that the yield of
3aa could be improved further to 62% if the reaction was conducted under an air atmosphere
(Table 1, entry 12). Subsequent solvent screening revealed that PhCF3 was the most efficient
medium for the reaction (Table 1, entries13–15). We suspected that in polar solvents such as DMF
and DMSO, protodecarboxylation is too fast and it became the main reaction pathway. With a
slight increase in the loading of silver salt from 1.0 equiv to 1.5 equiv, the yield of 3aa was
increased to 74% (Table 1, entries 16, 17). Moreover, we attempted to conduct the reaction in the
presence of catalytic amounts of Ag2CO3 and a stoichiometric amount of K2S2O8. Unfortunately,
3aa was obtained only in 14% yield (Table 1, entry 18). Further improvement was achieved by
increasing the amount of 1,10-phenanthroline and 3aa could be isolated in 81% yield (Table 1,
entries 19, 20). Finally, it was found that decreasing the reaction temperature to 150 oC resulted in
3aa with a slightly reduced yield (Table 1, entry 21).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 2. Substrate Scope of the Aromatic Carboxylic Acidsa
aReaction conditions: 1 (0.3 mmol), 2a (2.0 equiv), Ag2CO3 (1.5 equiv), 1,10-phenanthroline (0.6
equiv), PhCF3 (3 mL), 160 °C, air, 18 h. Isolated yield. bReaction time was 36 h.
With the optimized conditions in hand, we next sought to explore the substrate scope of the
decarboxylative sulfonylation reaction with respect to aryl carboxylic acids (Table 2). It was found
that 2-nitrobenzoic acids substituted with electron-withdrawing (chloro, bromo, and
trifluoromethyl) or electron-donating (methyl and methoxy) groups on the aryl rings all reacted
ACS Paragon Plus Environment

Page 5 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
satisfactorily with sodium 4-methylbenzenesulfinate (2a) to give the corresponding products in
moderate to good yields (3aa-3la). It should be mentioned that sterically hindered substrate 1h
could be subjected to the decarboxylative sulfonylation reaction, delivering the desired product
3ha in 52% yield. We were delighted to find that the scope of carboxylic acids was not limited to
2-nitrobenzoic acid derivatives in this protocol. The reactions of 2-(methylsulfonyl)benzoic acid
and 2-fluorobenzoic acid proceeded smoothly to produce the corresponding decarboxylative
sulfonylation products 3ma and 3na, albeit with slightly lower yields. Moreover,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2-chloro-5-nitrobenzoic
acid,
3-methylbenzofuran-2-carboxylic
acid,
and
3-chlorobenzo[b]thiophene-2-carboxylic acid were also viable substrates, affording 3oa, 3pa, and
3qa in 43%, 41%, and 39% yield, respectively. It is worth noting that the presence of halogen
atoms (chloro and bromo) in products 3 offers the opportunity for further synthetic
transformations via cross-coupling reactions (3ca-3ea, 3la and 3oa). We were disappointed to find
that parent benzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-methylbenzoic acid, as well as
the 2-methoxybenzoic acid could not afford the corresponding decarboxylative sulfonylation
products under standard conditions. The reason why 2-nitrobenzoic acid derivatives provided
better results than other aryl carboxylic acid derivatives may be due to the fact that the ortho-nitro
groups can stabilize Ar-Ag species formed in situ after decarboxylation through Ag-O
coordination.20
Table 3. Substrate Scope of the Sodium Sulfinatesa
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 23
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
aReaction conditions: 1a (0.3 mmol), 2 (2.0 equiv), Ag2CO3 (1.5 equiv), 1,10-phenanthroline (0.6
equiv), PhCF3 (3 mL), 160 °C, air, 18 h. Isolated yield.
Next, the scope of the sodium sulfinates was investigated. As shown in Table 3, a variety of
sodium sulfinates were compatible with this transformation. Functional groups such as halogens
(3ad, 3ae, 3ag-3ai), trifluoromethyl (3aj) and nitro (3af and 3ak) attached to the aryl ring were all
well tolerated, giving the desired products in moderate to good yields. From the table, we can see
product 3ac derived from an ortho-substituted sodium sulfinate was obtained with lower yield,
which may be due to steric hindrance. Furthermore, sodium naphthalene-2-sulfinate could also
participate in the reaction to afford the corresponding product 3an in 78% yield. It should be noted
that sodium cyclopropanesulfinate, an aliphatic sodium sulfinate, also proved to be a good
substrate, delivering the desired product 3ao in 67% yield. Unfortunately, CF3SO2Na and
CH3SO2Na were found to be incompatible for the system, perhaps due to the instability of the
corresponding alkyl sulfone radical intermediate.
Scheme 1. Derivatization of the Obtained Product
Subsequently, we performed several experiments to highlight the synthetic utility of the
ACS Paragon Plus Environment

Page 7 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
decarboxylative sulfonylation product (Scheme 1). 2-Nitro-4-(phenylethynyl)-1-tosylbenzene (4a)
could be produced in 94% yield via Sonogashira cross-coupling (Scheme 1a). Moreover, Suzuki
coupling of 3ea with phenylboronic acid could afford 3-nitro-4-tosyl-1,1'-biphenyl (4b) in 89%
7
8
9
yield (Scheme 1b).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 2. Mechanism Experiments
Preliminary mechanism experiments were conducted to gain insights into the reaction (Scheme
2). When radical scavenger TEMPO or BHT was added to the reaction mixture under the standard
conditions, the formation of 3aa was totally suppressed (Scheme 2a). This result reveals that a
radical pathway is likely to be involved in the reaction. It should be noted that in both cases
nitrobenzene could be detected by GC-MS analysis (please see Supporting Information), however,
we did not detect the TEMPO-bound adduct in the presence of radical scavenger TEMPO.
Therefore, we attempted to trap the radical intermediate with 1,1-diphenylethylene. Much to our
satisfaction, vinyl sulfone 5 could be isolated in 18% yield, suggesting the involvement of sulfonyl
radicals (Scheme 2b).
Scheme 3. Possible Reaction Mechanism
On the basis of the above investigations and previous literature reports,21 a plausible reaction
mechanism is proposed in Scheme 3. Initially, the reaction of aromatic carboxylic acid 1 with the
Ag2CO3 gives silver carboxylate A, which in turn affords the aryl-Ag(I) species B by the loss of
a molecule of carbon dioxide. Meanwhile, sodium sulfinate 2 is oxidized by Ag(I) to generate an
oxygen-centered radical C, which could be easily resonated to sulfonyl radical D. Subsequently,
the sulfonyl radical D reacts with aryl-Ag(I) species B to provide the Ag(II) intermediate E.
Finally, reductive elimination of E gives the decarboxylative sulfonylation product 3. Since it is
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 23
1
2
3
well known that Ag-catalyzed proto-decarboxylation of 2-nitrobenzoic acid can proceed around
4
5
o
120 C and our reactions are ran at significantly higher temperature. We suspect that higher
6
7
8
9
temperature could be beneficial for the formation of Ag (II) intermediate E via the reaction of
sulfonyl radical D with aryl-Ag (I) species B.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
In conclusion, we have developed a novel and efficient strategy for the synthesis of sulfones via
silver-promoted decarboxylative sulfonylation reaction of aromatic carboxylic acids with sodium
sulfinates. This reaction proceeds readily under air atmosphere and is simple to operate. This
transformation uses readily available aromatic carboxylic acids and sodium sulfinates as starting
materials, and a variety of sulfones could be efficiently obtained in moderate to good yields.
Preliminary mechanism investigations revealed that the reaction probably proceeds through a
radical pathway. Further studies on extending the substrate scope are underway, and the results
will be forthcoming.
EXPERIMENTAL SECTION
General. Unless otherwise noted, all reagents were obtained from commercial suppliers and used
without further purification. The sodium sulfinates were prepared according the previous reports.22
1
Products were purified by column chromatography on 200-300 mesh silica gel, SiO2. H and 13C
NMR spectra were measured on a 400 MHz NMR spectrometer using CDCl3 or DMSO-d6 as the
solvent. The chemical shifts are given in δ relative to TMS, and the coupling constants are given
in Hertz. The peak patterns are indicated as follows: s, singlet; d, doublet; t, triplet; q, quartet; m,
multiplet; qui, quintet; sxt, sextet. The high-resolution mass spectra (HRMS) analyses were
conducted using a TOF MS instrument with an ESI source. Melting points were measured by a
melting point instrument and were uncorrected.
General Procedure for Silver-Promoted Decarboxylative Sulfonylation Reaction of Aromatic
Carboxylic Acids with Sodium Sulfinates. Benzoic acid 1 (0.3 mmol), Ag2CO3 (124.1 mg, 0.45
mmol), 1,10-phenanthroline (32.4 mg, 0.18 mmol), sodium sulfinate 2 (0.6 mmol) and PhCF3 (3.0
mL) were added to a 25 mL Schlenk flask equipped with a high-vacuum PTFE valve-to-glass seal.
o
Then the flask was sealed under air and stirred at 160 C (oil bath) for 18 h. The cooled reaction
mixture was diluted with DCM (10 mL) and filtered through a short pad of silica gel, which then
was washed with more DCM (3 × 10 mL). The solvent was removed in vacuum and the product
was isolated through column chromatography to afford the desired product 3.
ACS Paragon Plus Environment

Page 9 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
1-Nitro-2-tosylbenzene (3aa). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 8/1, v/v) afforded 3aa as a white solid (67.3 mg, 81% yield); mp 151-153 oC;
1H NMR (400 MHz, CDCl3): δ 8.32 (d, J = 7.2 Hz, 1H), 7.86 (d, J = 7.6 Hz, 2H), 7.78-7.68 (m,
3H), 7.35 (d, J = 7.6 Hz, 2H), 2.43 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.4, 145.0,
137.3, 134.8, 134.4, 132.4, 131.4, 129.7, 128.3, 124.6, 21.6; HRMS (ESI, m/z) calcd for
C13H12NO4S [M + H]+ 278.0482, found 278.0490.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Larger-Scale Synthesis of 3aa. 2-Nitrobenzoic acid 1a (334.2 mg, 2.0 mmol), Ag2CO3 (827.2 mg,
3.0 mmol), 1,10-phenanthroline (216.0 mg, 1.2 mmol), sodium 4-methylbenzenesulfinate 2a
(712.7 mg, 4.0 mmol) and PhCF3 (20 mL) were added to a 50 mL Schlenk flask equipped with a
o
high-vacuum PTFE valve-to-glass seal. Then the flask was sealed under air and stirred at 160 C
(oil bath) for 18 h. The cooled reaction mixture was diluted with DCM (20 mL) and filtered
through a short pad of silica gel, which then was washed with more DCM (3 × 10 mL). The
solvent was removed in vacuum and the product was isolated through column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) to afford 3aa (388.2 mg, 70% yield).
1-Methyl-2-nitro-3-tosylbenzene (3ba). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ba as a light yellow solid (50.6 mg, 58%
yield); mp 129-131 oC; 1H NMR (400 MHz, CDCl3): δ 8.02-8.01 (m, 1H), 7.82 (d, J = 7.6 Hz, 2H),
7.54-7.53 (m, 2H), 7.33 (d, J = 7.6 Hz, 2H), 2.41 (s, 3H), 2.30 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 148.2, 145.1, 137.4, 136.6, 133.3, 131.4, 130.4, 129.8, 128.3, 128.2, 21.6, 17.0; HRMS
(ESI, m/z) calcd for C14H13NO4SNa [M + Na]+ 314.0457, found 314.0465.
1-Chloro-2-nitro-3-tosylbenzene (3ca). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ca as a white solid (57.8 mg, 62% yield); mp
o
1
150-152 C; H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 8.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 2H),
7.72 (d, J = 8.0 Hz, 1H), 7.60 (t, J = 8.0 Hz, 1H), 7.35 (d, J = 7.6 Hz, 2H), 2.43 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 146.4, 145.7, 136.7, 135.5, 135.2, 131.3, 130.1, 129.0, 128.4, 127.1,
21.7; HRMS (ESI, m/z) calcd for C13H10ClNO4SNa [M + Na]+ 333.9911, found 333.9902.
4-Chloro-2-nitro-1-tosylbenzene (3da). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3da as a white solid (63.4 mg, 68% yield); mp
o
1
106-108 C; H NMR (400 MHz, CDCl3): δ 8.26 (d, J = 8.4 Hz, 1H), 7.84 (d, J = 7.6 Hz, 2H),
7.72 (d, J = 8.4 Hz, 1H), 7.68 (s, 1H), 7.35 (d, J = 7.6 Hz, 2H), 2.43 (s, 3H); 13C{1H} NMR (100
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 23
1
2
3
4
5
MHz, CDCl3): δ 148.7, 145.3, 140.7, 137.0, 133.3, 132.6, 132.4, 129.8, 128.4, 124.8, 21.6; HRMS
(ESI, m/z) calcd for C13H10ClNO4SNa [M + Na]+ 333.9911, found 333.9915.
6
7
8
9
4-Bromo-2-nitro-1-tosylbenzene (3ea). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 10/1, v/v) afforded 3ea as a white solid (77.7 mg, 73% yield); mp
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
1
114-116 C; H NMR (400 MHz, CDCl3): δ 8.18 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H),
7.85-7.83(m, 3H), 7.36 (d, J = 7.6 Hz, 2H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
148.5, 145.3, 136.9, 135.5, 133.8, 132.6, 129.8, 128.7, 128.4, 127.6, 21.7; HRMS (ESI, m/z) calcd
for C13H10BrNO4SNa [M + Na]+ 377.9406, found 377.9409.
2-Nitro-1-tosyl-4-(trifluoromethyl)benzene (3fa). Purification by column chromatography on silica
gel (petroleum ether/ethyl acetate = 20/1, v/v) afforded 3fa as a white solid (68.3 mg, 66% yield);
mp 133-135 oC; 1H NMR (400 MHz, CDCl3): δ 8.48 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 8.4 Hz, 1H),
7.95 (s, 1H), 7.87 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 7.6 Hz, 2H), 2.45 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 148.5, 145.8, 138.3, 136.3, 136.2 (q, J = 34.9 Hz), 132.4, 130.0, 129.2 (q, J = 3.5
Hz), 128.7, 122.0 (q, J = 3.5 Hz), 121.9 (q, J = 272.1 Hz), 21.7; 19F NMR (376 MHz, CDCl3): δ
-63.3; HRMS (ESI, m/z) calcd for C14H10F3NO4SNa [M + Na]+ 368.0175, found 368.0178.
4-Methoxy-2-nitro-1-tosylbenzene (3ga). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 4/1, v/v) afforded 3ga as a white solid (66.3 mg, 72% yield); mp
o
1
118-120 C; H NMR (400 MHz, CDCl3): δ 8.24 (d, J = 8.8 Hz, 1H), 7.83 (d, J = 7.6 Hz, 2H),
7.33 (d, J = 8.0 Hz, 2H), 7.19-7.17 (m, 2H), 3.91 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 163.7, 149.8, 144.5, 138.1, 133.3, 129.6, 128.0, 126.2, 116.9, 110.6, 56.4, 21.6; HRMS
(ESI, m/z) calcd for C14H14NO5S [M + H]+ 308.0587, found 308.0583.
1-Methyl-3-nitro-2-tosylbenzene (3ha). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ha as a white solid (45.4 mg, 52% yield); mp
o
1
132-134 C; H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 7.6 Hz, 2H), 7.56 (t, J = 7.6 Hz, 1H),
7.40-7.34 (m, 4H), 2.58 (s, 3H), 2.43 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 151.1, 145.2,
141.5, 137.2, 135.1, 133.9, 131.1, 129.8, 127.9, 121.9, 21.6, 21.5; HRMS (ESI, m/z) calcd for
C14H14NO4S [M + H]+ 292.0638, found 292.0640.
4-Methoxy-1-nitro-2-tosylbenzene (3ia). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 4/1, v/v) afforded 3ia as a white solid (65.4 mg, 71% yield); mp
151-153 oC; 1H NMR (400 MHz, CDCl3): δ 7.90 (s, 1H), 7.86-7.83 (m, 3H), 7.34 (d, J = 8.0 Hz,
ACS Paragon Plus Environment

Page 11 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
2H), 7.13 (d, J = 8.8 Hz, 1H), 3.97 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
162.6, 144.7, 141.0, 137.4, 129.5, 128.2, 127.7, 117.9, 117.2, 56.5, 21.6; HRMS (ESI, m/z) calcd
for C14H14NO5S [M + H]+ 308.0587, found 308.0590.
8
9
1,2-Dimethoxy-4-nitro-5-tosylbenzene (3ja). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 4/1, v/v) afforded 3ja as a white solid (63.7 mg, 63% yield); mp
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
1
167-169 C; H NMR (400 MHz, CDCl3): δ 7.83-7.81 (m, 3H), 7.35-7.31 (m, 3H), 4.07 (s, 3H),
3.96 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 152.3, 151.6, 144.4, 141.8, 138.1,
129.5, 128.1, 127.9, 112.7, 108.1, 56.9, 56.8, 21.6; HRMS (ESI, m/z) calcd for C15H16NO6S [M +
H]+ 338.0693, found 338.0691.
4-Methyl-1-nitro-2-tosylbenzene (3ka). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 10/1, v/v) afforded 3ka as a white solid (53.3 mg, 61% yield); mp
168-170 oC; 1H NMR (400 MHz, CDCl3): δ 8.15 (s, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.65 (d, J = 8.0
Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 7.6 Hz, 2H), 2.54 (s, 3H), 2.43 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 146.2, 144.8, 144.0, 137.6, 134.8, 134.6, 131.8, 129.6, 128.3, 124.9,
21.7, 21.5; HRMS (ESI, m/z) calcd for C14H14NO4S [M + H]+ 292.0638, found 292.0632.
4-Chloro-1-nitro-2-tosylbenzene (3la). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3la as a white solid (60.6 mg, 65% yield); mp
180-182 oC; 1H NMR (400 MHz, CDCl3): δ 8.32 (s, 1H), 7.86 (d, J = 7.6 Hz, 2H), 7.71-7.66 (m,
2H), 7.37 (d, J = 7.6 Hz, 2H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 146.5, 145.5,
139.0, 136.8, 136.7, 134.1, 131.4, 129.8, 128.6, 126.1, 21.7; HRMS (ESI, m/z) calcd for
C13H10ClNO4SNa [M + Na]+ 333.9911, found 333.9910.
1-(Methylsulfonyl)-2-tosylbenzene (3ma). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ma as a white solid (35.3 mg, 38% yield); mp
o
1
151-153 C; H NMR (400 MHz, CDCl3): δ 8.52 (d, J = 7.6 Hz, 1H), 8.32 (d, J = 7.6 Hz, 1H),
7.88-7.79 (m, 4H), 7.29 (d, J = 7.6 Hz, 2H), 3.51 (s, 3H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 144.5, 140.8, 139.8, 138.0, 134.2, 134.0, 133.1, 132.4, 129.4, 128.3, 45.6, 21.6; HRMS
(ESI, m/z) calcd for C14H15O4S2 [M + H]+ 311.0406, found 311.0399.
1-Fluoro-2-tosylbenzene(3na). Purification by column chromatography on silica gel (petroleum
ether/ethyl acetate = 8/1, v/v) afforded 3na as a white solid (27.0 mg, 36% yield); mp 110-112 oC;
1H NMR (400 MHz, CDCl3): δ 8.08 (t, J = 7.2 Hz, 1H), 7.89 (d, J = 7.6 Hz, 2H), 7.58-7.53 (m,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 23
1
2
3
4
5
6
7
8
9
1H), 7.32-7.28 (m, 3H), 7.08 (t, J = 9.2 Hz, 1H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
δ 159.1 (d, J = 255.5 Hz), 144.7, 137.9, 135.7 (d, J = 8.4 Hz), 129.7, 129.6, 128.1, 124.5 (d, J =
3.8 Hz), 117.2 (d, J = 21.1 Hz), 21.6; 19F NMR(376 MHz, CDCl3): δ −107.8; HRMS (ESI, m/z)
calcd for C13H12FO2S [M + H]+ 251.0537, found 251.0541.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1-Chloro-4-nitro-2-tosylbenzene(3oa). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3oa as a white solid (40.1 mg, 43% yield); mp
o
1
188-190 C; H NMR (400 MHz, CDCl3): δ 9.17 (d, J = 2.4 Hz, 1H), 8.34 (dd, J = 8.8, 2.4 Hz,
1H), 7.87 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.8 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 2.44 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 146.4, 145.6, 140.7, 139.5, 135.6, 133.3, 129.8, 129.0, 128.5,
126.1, 21.7; HRMS (ESI, m/z) calcd for C13H11ClNO4S [M + H]+ 312.0092, found 312.0090.
3-Methyl-2-tosylbenzofuran (3pa). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 50/1, v/v) afforded 3pa as a white solid (35.2 mg, 41% yield); mp
o
1
112-114 C; H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 7.6 Hz, 2H), 7.59 (d, J = 7.6 Hz, 1H),
7.47-7.40 (m, 2H), 7.34-7.28 (m, 3H), 2.64 (s, 3H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 154.6, 145.7, 144.9, 137.6, 129.9, 128.2, 128.0, 127.7, 123.6, 123.5, 121.3, 112.2, 21.6,
8.6; HRMS (ESI, m/z) calcd for C16H15O3S [M + H]+ 287.0736, found 287.0758.
3-Chloro-2-tosylbenzo[b]thiophene (3qa). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 50/1, v/v) afforded 3qa as a white solid (37.7 mg, 39% yield); mp
169-171 oC; 1H NMR (400 MHz, CDCl3): δ 8.00 (d, J = 8.4 Hz, 2H), 7.86-7.81 (m, 2H), 7.54-7.45
(m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 145.1, 138.5,
137.3, 136.6, 136.5, 129.8, 128.4, 128.2, 125.9, 124.8, 123.6, 122.8, 21.6; LRMS (EI, 70 ev) m/z
(%):322 (M+, 56), 281 (33), 207 (73), 139 (100).
1-Nitro-2-(phenylsulfonyl)benzene (3ab). Purification by column chromatography on silica gel
(petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ab as a white solid (65.5 mg, 83% yield); mp
o
1
145-147 C; H NMR (400 MHz, CDCl3): δ 8.35 (d, J = 7.2 Hz, 1H), 7.97 (d, J = 7.6 Hz, 2H),
7.80-7.71 (m, 3H), 7.63 (t, J = 7.6 Hz, 1H), 7.55 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3): δ 148.4, 140.3, 134.6, 134.4, 133.8, 132.5, 131.5, 129.1, 128.2, 124.7; HRMS (ESI, m/z)
calcd for C12H9NO4SNa [M + Na]+ 286.0144, found 286.0148.
1-Methyl-2-((2-nitrophenyl)sulfonyl)benzene (3ac). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ac as a white solid (44.0 mg, 53%
ACS Paragon Plus Environment

Page 13 of 23
The Journal of Organic Chemistry
1
2
3
o
1
yield); mp 139-141 C; H NMR (400 MHz, CDCl3): δ 8.35 (d, J = 7.2 Hz, 1H), 8.06 (d, J = 8.0
Hz, 1H), 7.83-7.78 (m, 3H), 7.53 (t, J = 7.2 Hz, 1H), 7.42 (t, J = 7.6 Hz, 1H), 7.27 (d, J = 7.6 Hz,
1H), 2.47 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.4, 138.5, 137.2, 134.6, 134.4, 133.9,
132.5, 132.4, 131.8, 130.0, 126.3, 125.1, 20.2; HRMS (ESI, m/z) calcd for C13H12NO4S [M + H]+
278.0482, found 278.0476.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1-((3-Chlorophenyl)sulfonyl)-2-nitrobenzene (3ad). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ad as a white solid (57.9 mg, 65%
yield); mp 130-132 oC; 1H NMR (400 MHz, CDCl3): δ 8.38 (d, J = 6.4 Hz, 1H), 7.92 (s, 1H), 7.88
(d, J = 7.6 Hz, 1H), 7.83-7.79 (m, 3H), 7.60 (d, J = 7.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 148.5, 142.2, 135.3, 135.0, 133.9, 132.8, 131.8, 130.4, 128.1, 126.3,
125.0; HRMS (ESI, m/z) calcd for C12H8ClNO4SNa [M + Na]+ 319.9755, found 319.9758.
1-((3-Bromophenyl)sulfonyl)-2-nitrobenzene (3ae). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ae as a white solid (67.5 mg, 66%
yield); mp 130-132 oC; 1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 6.8 Hz, 1H), 8.06 (s, 1H), 7.92
(d, J = 8.0 Hz, 1H), 7.85-7.79 (m, 3H), 7.75 (d, J = 8.0 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 148.5, 142.3, 136.8, 135.0, 133.9, 132.8, 131.8, 130.8, 130.6, 126.8,
125.0, 122.9; HRMS (ESI, m/z) calcd for C12H8BrNO4SNa [M + Na]+ 363.9250, found 363.9247.
1-Nitro-2-((3-nitrophenyl)sulfonyl)benzene (3af). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 4/1, v/v) afforded 3af as a light yellow solid (53.6 mg,
o
1
58% yield); mp 172-174 C; H NMR(400 MHz, DMSO-d6): δ 8.64 (s, 1H), 8.59 (d, J = 8.0 Hz,
1H), 8.52 (d, J = 6.4 Hz, 1H), 8.42 (d, J = 7.6 Hz, 1H), 8.10 (d, J = 6.8 Hz, 1H), 8.04-7.98 (m, 3H);
13C{1H} NMR (100 MHz, DMSO-d6): δ 148.0, 147.9, 141.5, 136.7, 133.8, 133.7, 132.2, 131.8,
131.4, 129.0, 125.4, 122.5; HRMS (ESI, m/z) calcd for C12H8N2O6SNa [M + Na]+ 330.9995,
found 330.9991.
1-((4-Fluorophenyl)sulfonyl)-2-nitrobenzene (3ag). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ag as a white solid (59.9 mg, 71%
yield); mp 139-141 oC; 1H NMR (400 MHz, CDCl3): δ 8.35 (d, J = 7.2 Hz, 1H), 8.02-7.99 (m, 2H),
7.82-7.74 (m, 3H), 7.24 (t, J = 8.0 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3): δ 165.8 (d,
J=255.6 Hz), 148.5, 136.4 (d, J=3.1 Hz), 134.7, 134.5, 132.6, 131.5, 131.3 (d, J=9.7 Hz), 124.8,
116.5 (d, J=22.7 Hz); 19F NMR(376 MHz, CDCl3): δ −102.7; HRMS (ESI, m/z) calcd for
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 23
1
2
3
C12H8FNO4SNa [M + Na]+ 304.0050, found 304.0051.
4
5
6
7
8
9
1-((4-Chlorophenyl)sulfonyl)-2-nitrobenzene (3ah). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ah as a light yellow solid (68.6 mg,
77% yield); mp 135-137 oC; 1H NMR (400 MHz, CDCl3): δ 8.35 (d, J = 6.8 Hz, 1H), 7.91 (d, J =
8.0 Hz, 2H), 7.82-7.74 (m, 3H), 7.53 (d, J = 7.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3): δ
148.4, 140.6, 138.8, 134.9, 134.2, 132.7, 131.6, 129.7, 129.4, 124.9; HRMS (ESI, m/z) calcd for
C12H8ClNO4SNa [M + Na]+ 319.9755, found 319.9756.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1-((4-Bromophenyl)sulfonyl)-2-nitrobenzene (3ai). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 10/1, v/v) afforded 3ai as a white solid (65.5 mg, 64%
yield); mp 135-137 oC; 1H NMR (400 MHz, CDCl3): δ 8.36 (d, J = 6.8 Hz, 1H), 7.84-7.77 (m, 5H),
7.70 (d, J = 7.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.5, 139.4, 134.8, 134.2, 132.7,
132.4, 131.6, 129.8, 129.2, 124.9; HRMS (ESI, m/z) calcd for C12H8BrNO4SNa [M + Na]+
363.9250, found 363.9252.
1-Nitro-2-((4-(trifluoromethyl)phenyl)sulfonyl)benzene
(3aj).
Purification
by
column
chromatography on silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3aj as a white
o
1
solid (71.5 mg, 72% yield); mp 121-123 C; H NMR (400 MHz, CDCl3): δ 8.42 (d, J = 7.2 Hz,
1H), 8.10 (d, J = 8.0 Hz, 2H), 7.84-7.82 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.6,
144.1, 135.3 (q, J = 33.0 Hz), 135.2, 133.7, 132.9, 131.9, 128.7, 126.2 (q, J = 3.6 Hz), 125.1,
123.0 (q, J = 271.4 Hz); 19F NMR (376 MHz, CDCl3): δ -63.2; HRMS (ESI, m/z) calcd for
C13H8F3NO4SNa [M + Na]+ 354.0018, found 354.0019.
1-Nitro-2-((4-nitrophenyl)sulfonyl)benzene (3ak). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 4/1, v/v) afforded 3ak as a light yellow solid (47.1 mg,
51% yield); mp 202-204 oC; 1H NMR (400 MHz, DMSO-d6): δ 8.50-8.46 (m, 3H), 8.22 (d, J = 8.0
Hz, 2H), 8.11 (d, J = 6.8 Hz, 1H), 8.05-8.03 (m, 2H); 13C{1H} NMR (100 MHz, DMSO-d6): δ
150.6, 147.9, 145.3, 136.8, 133.8, 132.1, 131.2, 129.2, 125.5, 124.9; HRMS (ESI, m/z) calcd for
C12H8N2O6SNa [M + Na]+ 330.9995, found 330.9987.
1-((4-Methoxyphenyl)sulfonyl)-2-nitrobenzene (3al). Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 4/1, v/v) afforded 3al as a white solid (46.6 mg, 53%
o
1
yield); mp 151-153 C; H NMR (400 MHz, CDCl3): δ 8.30 (d, J = 7.2 Hz, 1H), 7.92 (d, J = 7.6
Hz, 2H), 7.77-7.67 (m, 3H), 7.01 (d, J = 7.6 Hz, 2H), 3.87 (s, 3H); 13C{1H} NMR (100 MHz,
ACS Paragon Plus Environment

Page 15 of 23
The Journal of Organic Chemistry
1
2
3
4
5
CDCl3): δ 163.9, 148.3, 135.2, 134.2, 132.3, 131.6, 131.2, 130.8, 124.5, 114.3, 55.7; HRMS (ESI,
m/z) calcd for C13H12NO5S [M + H]+ 294.0431, found 294.0427.
6
7
8
9
1-((4-(Tert-butyl)phenyl)sulfonyl)-2-nitrobenzene (3am). Purification by column chromatography
on silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3am as a white solid (54.6 mg,
57% yield); mp 126-128 oC; 1H NMR (400 MHz, CDCl3): δ 8.34 (d, J = 7.2 Hz, 1H), 7.91 (d, J =
7.6 Hz, 2H), 7.79-7.70 (m, 3H), 7.56 (d, J = 7.6 Hz, 2H), 1.33 (s, 9H); 13C{1H} NMR (100 MHz,
CDCl3): δ 157.9, 148.4, 137.2, 134.9, 134.4, 132.4, 131.5, 128.2, 126.1, 124.6, 35.3, 31.0; HRMS
(ESI, m/z) calcd for C16H18NO4S [M + H]+ 320.0951, found 320.0949.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2-((2-Nitrophenyl)sulfonyl)naphthalene (3an). Purification by column chromatography on silica
gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3an as a light yellow solid (73.3 mg, 78%
yield); mp 143-145 oC; 1H NMR (400 MHz, CDCl3): δ 8.60 (s, 1H), 8.41 (d, J = 7.6 Hz, 1H), 8.01
(d, J = 8.0 Hz, 1H), 7.97 (d, J = 8.8 Hz, 1H), 7.89 (d, J = 8.4 Hz, 2H), 7.80-7.69 (m, 3H),
7.67-7.59 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.4, 137.1, 135.2, 134.6, 134.5, 132.5,
131.9, 131.6, 130.3, 129.6, 129.5, 129.3, 127.9, 127.7, 124.7, 122.6; HRMS (ESI, m/z) calcd for
C16H11NO4SNa [M + Na]+ 336.0301, found 336.0304.
1-(Cyclopropylsulfonyl)-2-nitrobenzene (3ao). Purification by column chromatography on silica
gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 3ao as an orange solid (45.6 mg, 67% yield);
o
1
mp 95-97 C; H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 7.2 Hz, 1H), 7.84 (d, J = 7.2 Hz, 1H),
7.81-7.74 (m, 2H), 3.28-3.23 (m, 1H), 1.41-1.40 (m, 2H), 1.15-1.13 (m, 2H); 13C{1H} NMR (100
MHz, CDCl3): δ 149.1, 134.3, 134.0, 132.6, 131.2, 124.9, 33.0, 6.8; HRMS (ESI, m/z) calcd for
C9H9NO4SNa [M + Na]+ 250.0144, found 250.0144.
2-Nitro-4-(phenylethynyl)-1-tosylbenzene (4a). 4-Bromo-2-nitro-1-tosylbenzene 3ea (71.2 mg, 0.2
mmol), copper(I) iodide (1.5 mg, 0.008 mmol), and bis(triphenylphosphine) palladium(II)
dichloride (5.6 mg, 0.008 mmol) were added to a 25 mL Schlenk flask equipped with a
high-vacuum PTFE valve-to-glass seal. The tube was evacuated and backfilled with N2 three times
after which triethylamine (40.5 mg, 0.4 mmol) and THF (1 mL) were added via syringe. After 5
min at room temperature, the phenylacetylene (28.6 mg, 0.28 mmol) was added. The resulting
mixture was stirred at 80 °C (oil bath) for 12 h. It was then cooled to room temperature, and the
reaction mixture was quenched with H2O (20 mL), extracted with DCM (20 mL × 3), washed with
brine. The combined organic layers were dried over anhydrous Na2SO4, filtered, and concentrated.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 23
1
2
3
Purification by column chromatography on silica gel (petroleum ether/ethyl acetate = 8/1, v/v)
4
5
6
7
8
9
o
1
afforded 4a as a light yellow solid (70.9 mg, 94% yield); mp 176-178 C; H NMR (400 MHz,
CDCl3): δ 8.28 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 7.6 Hz, 2H), 7.83-7.80 (m, 2H), 7.54 (d, J = 7.2
Hz, 2H), 7.41-7.35 (m, 5H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.4, 145.1, 137.3,
134.6, 133.4, 131.9, 131.4, 130.3, 129.8, 129.7, 128.6, 128.4, 127.0, 121.3, 96.1, 85.7, 21.7;
HRMS (ESI, m/z) calcd for C21H16NO4S [M + H]+ 378.0795, found 378.0790.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3-Nitro-4-tosyl-1,1'-biphenyl (4b). 4-Bromo-2-nitro-1-tosylbenzene 3ea (71.2 mg, 0.2 mmol),
phenylboronic acid (29.3 mg, 0.24 mmol), K2CO3 (55.3 mg, 0.4 mmol), and Pd(PPh3)4 (11.6 mg,
0.01 mmol) were added to a 25 mL Schlenk flask equipped with a high-vacuum PTFE
valve-to-glass seal. The tube was evacuated and backfilled with N2 three times after which toluene
(1 mL) was added via syringe. The resulting mixture was stirred at 110 °C (oil bath) for 12 h. It
was then cooled to room temperature, and the reaction mixture was quenched with H2O (20 mL),
extracted with DCM (20 mL × 3), washed with brine. The combined organic layers were dried
over anhydrous Na2SO4, filtered, and concentrated. Purification by column chromatography on
silica gel (petroleum ether/ethyl acetate = 8/1, v/v) afforded 4b as a light yellow solid (62.8 mg,
o
1
89% yield); mp 174-176 C; H NMR (400 MHz, CDCl3): δ 8.37 (d, J = 8.0 Hz, 1H), 7.94-7.89
(m, 4H), 7.59 (d, J = 7.2 Hz, 2H), 7.52-7.49 (m, 3H), 7.36 (d, J = 7.6 Hz, 2H), 2.44 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 148.9, 147.8, 144.9, 137.6, 136.8, 132.9, 132.0, 130.3, 129.7,
129.4, 128.3, 127.2, 122.9, 21.6; HRMS (ESI, m/z) calcd for C19H16NO4S [M + H]+ 354.0795,
found 354.0793.
Mechanism Experiments (Scheme 2b). 2-Nitrobenzoic acid 1a (50.1 mg, 0.3 mmol), Ag2CO3
(124.1 mg, 0.45 mmol), 1,10-phenanthroline (32.4 mg, 0.18 mmol), sodium
4-methylbenzenesulfinate 2a (106.9 mg, 0.6 mmol), 1,1-diphenylethylene (162.1 mg, 0.9 mmol),
and PhCF3 (3.0 mL) were added to a 25 mL Schlenk flask equipped with a high-vacuum PTFE
valve-to-glass seal. Then the flask was sealed under air and stirred at 160 oC (oil bath) for 18 h. It
was then cooled to room temperature. The cooled reaction mixture was diluted with DCM (10 mL)
and filtered through a short pad of silica gel, which then was washed with more DCM (3 × 10 mL).
The solvent was removed in vacuum and the mixture was isolated through column
chromatography to afford 3aa (26.6 mg, 32% yield) and vinyl sulfone 5 (36.1 mg, 18% yield).
(2-Tosylethene-1,1-diyl)dibenzene (5).23 Purification by column chromatography on silica gel
ACS Paragon Plus Environment

Page 17 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
1
(petroleum ether/ethyl acetate = 15/1, v/v) afforded 5 as a colorless oil (36.1 mg, 18% yield); H
NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.0 Hz, 2H), 7.40-7.35 (m, 2H), 7.32-7.28 (m, 4H), 7.21 (d,
J = 7.2 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.0 Hz, 2H), 7.00 (s, 1H), 2.38 (s, 3H).
8
9
1
Supporting Information: Copies of H, 13C and 19F NMR Spectrum. This material is available
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
free of charge via the Internet at http://pubs.acs.org.
REFERENCES
(1) Patai, S.; Rappoprt, Z.; Stirling, C. J. M. The Chemistry of Sulfones and Sulfoxides; Wiley:
New York, 1988.
(2) (a) Almirante, L.; Polo, L.; Mugnaini, A.; Provinciali, E.; Rugarli, P.; Biancotti, A.; Gamba,
A.; Murmann, W. Derivatives of Imidazole. I. Synthesis and Reactions of
Imidazo[1,2-α]pyridines with Analgesic, Antiinflammatory, Antipyretic, and Anticonvulsant
Activity. J. Med. Chem. 1965, 8, 305–312. (b) Yazdanyar, S.; Boer, J.; Ingvarsson, G.;
Szepietowski, J. C.; Jemec, G. B. E. Dapsone Therapy for Hidradenitis Suppurativa: A Series
of 24 Patients. Dermatology 2011, 222, 342–346. (c) Chen, Y.; Guo, H.; Cai, M.; Geng, C.;
Yue, C.; Teng, C. Effect of Polyether Sulfone Resin on Micromorphology, Thermal,
Mechanical, and Dielectric Properties of Epoxy–Bismaleimide Composite Material. J.
Electron. Mater. 2018, 47, 6021–6027.
(3) (a) Nielsen, M.; Jacobsen, C. B.; Paixão, M. W.; Holub, N.; Jørgensen, K. A. Asymmetric
Organocatalytic Formal Alkynylation and Alkenylation of α,β-Unsaturated Aldehydes. J. Am.
Chem. Soc. 2009, 131, 10581–10586. (b) Wang, Q.-G.; Zhou, Q.-Q.; Deng, J.-G.; Chen, Y.-C.
An Asymmetric Allylic Alkylation-Smiles Rearrangement-Sulfinate Addition Sequence to
Construct Chiral Cyclic Sulfones. Org. Lett. 2013, 15, 4786–4789.
(4) Julia, M.; Paris, J.-M. Syntheses A L'aide De Sulfones V(+)-Methode De Synthese Generale
De Doubles Liaisons. Tetrahedron Lett. 1973, 14, 4833–4836.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 23
1
2
3
4
5
6
7
8
9
(5) (a) Xiao, F.; Chen, S.; Tian, J.; Huang, H.; Liu, Y.; Deng, G.-J. Chemoselective
Cross-coupling Reaction of Sodium Sulfinates with Phenols under Aqueous Conditions.
Green Chem. 2016, 18, 1538–1546. (b) Liu, N.-W.; Liang, S.; Manolikakes, G. Recent
Advances in the Synthesis of Sulfones. Synthesis 2016, 48, 1939–1973. (c) Liu, J; Zheng, L.
Recent Advances in Transition-Metal-Mediated Chelation-Assisted Sulfonylation of
Unactivated C–H Bonds. Adv. Synth. Catal. 2019, 361, 1710–1732. (d) Jiang, H.; Tang, X.;
Xu, Z.; Wang, H.; Han, K.; Yang, X.; Zhou, Y.; Feng, Y.-L.; Yu, X.-Y.; Gui, Q.
TBAI-Catalyzed Selective Synthesis of Sulfonamides and β-Aryl Sulfonyl Enamines:
Coupling of Arenesulfonyl Chlorides and Sodium Sulfinates with tert-Amines. Org. Biomol.
Chem. 2019, 17, 2715–2720.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(6) (a) Su, W. An Efficient Method for the Oxidation of Sulfides to Sulfomes. Tetrahedron Lett.
1994, 35, 4955–4958. (b) Bahrami, K.; Khodaei, M. M.; Arabi, M. S. TAPC-Promoted
Oxidation of Sulfides and Deoxygenation of Sulfoxides. J. Org. Chem. 2010, 75, 6208–6213.
(c) Kirihara, M.; Okada, T.; Sugiyama, Y.; Akiyoshi, M.; Matsunaga, T.; Kimura, Y. Sodium
Hypochlorite Pentahydrate Crystals (NaOCl·5H2O): A Convenient and Environmentally
Benign Oxidant for Organic Synthesis. Org. Process. Res. Dev. 2017, 21, 1925–1937.
(7) (a) Répichet, S.; Roux, C. L.; Hernandez, P.; Dubac, J. Bismuth(III)
Trifluoromethanesulfonate: An Efficient Catalyst for the Sulfonylation of Arenes. J. Org.
Chem. 1999, 64, 6479–6482. (b) Nara, S. J.; Harjani, J. R.; Salunkhe, M. M. Friedel-Crafts
Sulfonylation in 1-Butyl-3-methylimidazolium Chloroaluminate Ionic Liquids. J. Org. Chem.
2001, 66, 8616–8620.
(8) (a) Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M.; Bernini, R. Unsymmetrical Diaryl
Sulfones and Aryl Vinyl Sulfones through Palladium-Catalyzed Coupling of Aryl and Vinyl
Halides or Triflates with Sulfinic Acid Salts. J. Org. Chem. 2004, 69, 5608–5614. (b) Liu,
N.-W.; Liang, S.; Margraf, N.; Shaaban, S.; Luciano, V.; Drost, M.; Manolikakes, G.
Nickel-Catalyzed Synthesis of Diaryl Sulfones from Aryl Halides and Sodium Sulfinates. Eur.
J. Org. Chem. 2018, 1208–1210. (c) Zhao, J.; Niu, S.; Jiang, X.; Jiang, Y.; Zhang, X.; Sun, T.;
Ma, D. A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides
with Sulfinic Acid Salts under Mild Conditions. J. Org. Chem. 2018, 83, 6589–6598.
(9) (a) Qiu, G.; Zhou, K.; Wu, J. Recent Advances in the Sulfonylation of C–H Bonds with the
ACS Paragon Plus Environment

Page 19 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
Insertion of Sulfur Dioxide. Chem. Commun. 2018, 54, 12561–12569. (b) Ye, S.; Qiu, G.; Wu,
J. Inorganic Sulfites as the Sulfur Dioxide Surrogates in Sulfonylation Reactions. Chem.
Commun. 2019, 55, 1013–1019.
7
8
9
(10) For selected works, see: (a) Luo, Y.; Wu, J. Palladium-Catalyzed Decarboxylative
1,2-Addition of Carboxylic Acids to Aldehydes or Imines. Chem. Commun. 2010, 46,
3785–3787. (b) Rodríguez, N.; Gooßen, L. J. Decarboxylative Coupling Reactions: A
Modern Strategy for C–C-Bond Formation. Chem. Soc. Rev. 2011, 40, 5030–5048. (c) Shang,
R.; Liu, L. Transition Metal-Catalyzed Decarboxylative Cross-Coupling Reactions. Sci.
China: Chem. 2011, 54, 1670–1687. (d) Cornella, J.; Larrosa, I. Decarboxylative
Carbon–Carbon Bond-Forming Transformations of (Hetero)-aromatic Carboxylic Acids.
Synthesis 2012, 44, 653–676. (e) Wei, Y.; Hu, P.; Zhang, M.; Su, W. Metal-Catalyzed
Decarboxylative C–H Functionalization. Chem. Rev. 2017, 117, 8864–8907. (f) Patra, T.;
Maiti, D. Decarboxylation as the Key Step in C–C Bond-Forming Reactions. Chem.-Eur. J.
2017, 23, 7382–7401.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(11) For selected works, see: (a) Gooßen, L. J.; Deng, G.; Levy, L. M. Synthesis of Biaryls via
Catalytic Decarboxylative Coupling. Science 2006, 313, 662–664. (b) Bhadra, S.; Dzik, W. I.;
Gooßen, L. J. Decarboxylative Etherification of Aromatic Carboxylic Acids. J. Am. Chem.
Soc. 2012, 134, 9938–9941. (c) Song, B.; Knauber, T.; Gooßen, L. J. Decarboxylative
Cross-Coupling of Mesylates Catalyzed by Copper/Palladium Systems with Customized
Imidazolyl Phosphine Ligands. Angew. Chem., Int. Ed. 2013, 52, 2954–2958. (d) Tang, J.;
Biafora, A.; Gooßen, L. J. Catalytic Decarboxylative Cross-Coupling of Aryl Chlorides and
Benzoates without Activating ortho Substituents. Angew. Chem., Int. Ed. 2015, 54,
13130–13133.
(12) For selected works, see: (a) Hu, P.; Shang, Y.; Su, W. A General Pd-Catalyzed
Decarboxylative Cross-Coupling Reaction between Aryl Carboxylic Acids: Synthesis of
Biaryl Compounds. Angew. Chem., Int. Ed. 2012, 51, 5945–5949. (b) Kan, J.; Huang, S.; Lin,
J.; Zhang, M.; Su, W. Silver-Catalyzed Arylation of (Hetero)arenes by Oxidative
Decarboxylation of Aromatic Carboxylic Acids. Angew. Chem., Int. Ed. 2015, 54, 2199–2203.
(c) Zhang, Y.; Zhao, H.; Zhang, M.; Su, W. Carboxylic Acids as Traceless Directing Groups
for the Rhodium(III)-Catalyzed Decarboxylative C–H Arylation of Thiophenes. Angew.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 23
1
2
3
4
5
6
Chem., Int. Ed. 2015, 54, 3817–3821. (d) Jiang, Q.; Li, H.; Zhang, X.; Xu, B.; Su, W.
Pd-Catalyzed Decarboxylative Sonogashira Reaction via Decarboxylative Bromination. Org.
Lett. 2018, 20, 2424–2427.
7
8
9
(13) For selected works, see: (a) Myers, A. G.; Tanaka, D.; Mannion, M. R. Development of a
Decarboxylative Palladation Reaction and Its Use in a Heck-type Olefination of Arene
Carboxylates. J. Am. Chem. Soc. 2002, 124, 11250–11251. (b) Tanaka, D.; Myers, A. G.
Heck-type Arylation of 2-Cycloalken-1-Ones with Arylpalladium Intermediates Formed by
Decarboxylative Palladation and by Aryl Iodide Insertion. Org. Lett. 2004, 6, 433–436. (c)
Tanaka, D.; Romeril, S. P.; Myers, A. G. On the Mechanism of the Palladium(II)-Catalyzed
Decarboxylative Olefination of Arene Carboxylic Acids. Crystallographic Characterization of
Non-Phosphine Palladium(II) Intermediates and Observation of Their Stepwise
Transformation in Heck-like Processes. J. Am. Chem. Soc. 2005, 127, 10323–10333.
(14) For selected works, see: (a) Forgione, P.; Brochu, M.-C.; St-Onge, M.; Thesen, K. H.; Bailey,
M. D.; Bilodeau, F. Unexpected Intermolecular Pd-Catalyzed Cross-Coupling Reaction
Employing Heteroaromatic Carboxylic Acids as Coupling Partners. J. Am. Chem. Soc. 2006,
128, 11350–11351. (b) Shang, R.; Fu, Y.; Wang, Y.; Xu, Q.; Yu, H.-Z.; Liu, L.
Copper-Catalyzed Decarboxylative Cross-Coupling of Potassium Polyfluorobenzoates with
Aryl Iodides and Bromides. Angew. Chem., Int. Ed. 2009, 48, 9350–9354. (c) Cornella, J.; Lu,
P.; Larrosa, I. Intermolecular Decarboxylative Direct C-3 Arylation of Indoles with Benzoic
Acids. Org. Lett. 2009, 11, 5506–5509. (d) Luo, Y.; Pan X.; Wu, J. Silver-Catalyzed
Decarboxylative Halogenation of Carboxylic Acids. Tetrahedron Lett. 2010, 51, 6646–6648.
(e) Luo, J.; Lu, Y.; Liu, S.; Liu, J.; Deng, G.-J. Efficient One-Pot Synthesis of
Dibenzopyranones via a Decarboxylative Cross-Coupling and Lactonization Sequence. Adv.
Synth. Catal. 2011, 353, 2604–2608. (f) Fu, Z.; Li, Z.; Song, Y.; Yang, R.; Liu, Y.; Cai, H.
Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids
via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic
Conditions. J. Org. Chem. 2016, 81, 2794–2803.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(15) (a) Gooßen, L. J.; Rodríguez, N.; Linder, C. Decarboxylative Biaryl Synthesis from Aromatic
Carboxylates and Aryl Triflates. J. Am. Chem. Soc. 2008, 130, 15248–15249. (b) Wang, Z.;
Ding, Q.; He, X.; Wu, J. Pd-Catalyzed Decarboxylative Couplings of Arenecarboxylic Acids
ACS Paragon Plus Environment

Page 21 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
with Aryl Iodides. Tetrahedron 2009, 65, 4635–4638. (c) Tang, J.; Gooßen, L. J. Arylalkene
Synthesis via Decarboxylative Cross-Coupling of Alkenyl Halides. Org. Lett. 2014, 16,
2664–2667. (d) Katayev, D.; Exner, B.; Gooßen, L. J. Synthesis of Biaryls by
Decarboxylative Hiyama Coupling. ChemCatChem 2015, 7, 2028–2032.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(16) For selected works, see: (a) Zhang, Y.; Patel, S.; Mainolfi, N. Copper-Catalyzed
Decarboxylative C–N Coupling for N-arylation. Chem. Sci. 2012, 3, 3196–3199. (b) Chen, L.;
Ju, L.; Bustin, K. A.; Hoover, J. M. Copper-Catalyzed Oxidative Decarboxylative C–H
Arylation of Benzoxazoles with 2-Nitrobenzoic Acids. Chem. Commun. 2015, 51,
15059–15062. (c) Sheng, W.-J.; Ye, Q.; Yu, W.-B.; Liu, R.-R.; Xu, M.; Gao, J.-R.; Jia, Y.-X.
CuSO4-Mediated Decarboxylative C–N Cross-Coupling of Aromatic Carboxylic Acids with
Amides and Anilines. Tetrahedron Lett. 2015, 56, 599–601. (d) Patra, T.; Nandi, S.; Sahoo, S.
K.; Maiti, D. Copper Mediated Decarboxylative Direct C–H Arylation of Heteroarenes with
Benzoic Acids. Chem. Commun. 2016, 52, 1432–1435. (e) Li, M.; Hoover, J. M. Aerobic
Copper-Catalyzed Decarboxylative Thiolation. Chem. Commun. 2016, 52, 8733–8736.
(17) (a) Seo, S.; Slater, M.; Greaney, M. F. Decarboxylative C–H Arylation of Benzoic Acids
under Radical Conditions. Org. Lett. 2012, 14, 2650–2653. (b) Natarajan, P.; Chaudhary, R.;
Venugopalan, P. Silver(I)-Promoted ipso-Nitration of Carboxylic Acids by Nitronium
Tetrafluoroborate. J. Org. Chem. 2015, 80, 10498–10504.
(18) (a) Xie, K.; Yang, Z.; Zhou, X.; Li, X.; Wang, S.; Tan, Z.; An, X.; Guo, C.-C. Pd-Catalyzed
Decarboxylative Arylation of Thiazole, Benzoxazole, and Polyfluorobenzene with
Substituted Benzoic Acids. Org. Lett. 2010, 12, 1564–1567. (b) Wang, A.; Li, X.; Liu, J.; Gui,
Q.; Chen, X.; Tan, Z.; Xie, K. Synthesis of Biaryls via Pd-Catalyzed Decarboxylative
Coupling of Substituted Benzoic Acids with Phenylboronic Acids. Synth. Commun. 2014, 44,
289–295. (c) Hu, L.; Wang, D.; Chen, X.; Yu, L.; Yu, Y.; Tan, Z.; Zhu, G. Copper-Catalyzed
Decarboxylative Methylthiolation of Aromatic Carboxylate Salts with DMSO. Org. Biomol.
Chem. 2017, 15, 5674–5679. (d) Yu, Y.; Chen, X.; Wu, Q.; Liu, D.; Hu, L.; Yu, L.; Tan, Z.;
Gui, Q.; Zhu, G. Synthesis of Aryl Alkynes via Copper Catalyzed Decarboxylative
Alkynylation of 2-Nitrobenzoic Acids. J. Org. Chem. 2018, 83, 8556–8566.
(19) For selected works, see: (a) Singh, R.; Allam, B. K.; Singh, N.; Kumari, K.; Singh, S. K.;
Singh, K. N. A Direct Metal-Free Decarboxylative Sulfono Functionalization (DSF) of
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 23
1
2
3
4
5
6
7
8
9
Cinnamic Acids to α,β-Unsaturated Phenyl Sulfones. Org. Lett. 2015, 17, 2656–2659. (b)
Meesin, J.; Katrun, P.; Pareseecharoen, C.; Pohmakotr, M.; Reutrakul, V.; Soorukram, D.;
Kuhakarn, C. Iodine-Catalyzed Sulfonylation of Arylacetylenic Acids and Arylacetylenes
with Sodium Sulfinates: Synthesis of Arylacetylenic Sulfones. J. Org. Chem. 2016, 81,
2744–2752. (c) Xue, N.; Guo, R.; Tu, X.; Luo, W.; Deng, W.; Xiang, J. Efficient Synthesis of
Vinyl Sulfones by Manganese-Catalyzed Decarboxylative Coupling of Cinnamic Acids with
Aromatic Sulfinic Acid Sodium Salts. Synlett 2016, 27, 2695–2698. (d) Qian, P.; Bi, M.; Su,
J.; Zha, Z.; Wang, Z. Electrosynthesis of (E)-Vinyl Sulfones Directly from Cinnamic Acids
and Sodium Sulfinates via Decarboxylative Sulfono Functionalization. J. Org. Chem. 2016,
81, 4876–4882. (e) Cai, S.; Xu, Y.; Chen, D.; Li, L.; Chen, Q.; Huang, M.; Weng, W.
Visible-Light-Enabled Decarboxylative Sulfonylation of Cinnamic Acids with
Sulfonylhydrazides under Transition-Metal-Free Conditions. Org. Lett. 2016, 18, 2990–2993.
(f) Zhao, Y.; Lai, Y.-L.; Du, K.-S.; Lin, D.-Z.; Huang, J.-M. Electrochemical Decarboxylative
Sulfonylation of Cinnamic Acids with Aromatic Sulfonylhydrazides to Vinyl Sulfones. J. Org.
Chem. 2017, 82, 9655–9661.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(20) Xue, L.; Su, W.; Lin, Z. Mechanism of Silver- and Copper-Catalyzed Decarboxylation
Reactions of Aryl Carboxylic Acids. Dalton Trans. 2011, 40, 11926–11936.
(21) (a) Mitamura, Y.; Asada, Y.; Murakami, K.; Someya, H.; Yorimitsu, H.; Oshima, K.
Silver-Catalyzed Benzylation and Allylation of Tertiary Alkyl Bromides with Organozinc
Reagents. Chem. Asian J. 2010, 5, 1487–1493. (b) Fang, G.; Liu, J.; Shang, W.; Liu, Q.; Bi, X.
Silver(I)-Promoted Radical Sulfonylation of Allyl/Propargyl Alcohols: Efficient Synthesis of
γ-Keto Sulfones. Chem. Asian J. 2016, 11, 3334–3338. (c) Baur, A.; Bustin, K. A.; Aguilera,
E.; Petersen, J. L.; Hoover, J. M. Copper and Silver Benzoate and Aryl Complexes and Their
Implications for Oxidative Decarboxylative Coupling Reactions. Org. Chem. Front. 2017, 4,
519–524. (d) Crovak, R. A.; Hoover, J. M. A Predictive Model for the Decarboxylation of
Silver Benzoate Complexes Relevant to Decarboxylative Coupling Reactions. J. Am. Chem.
Soc. 2018, 140, 2434–2437. (e) Rao, W.; Jiang, L.-L.; Liu, X.-M.; Chen, M.-J.; Chen, F.-Y.;
Jiang, X.; Zhao, J.-X.; Zou, G.-D.; Zhou, Y.-Q.; Tang, L. Copper(II)-Catalyzed Alkene
Aminosulfonylation with Sodium Sulfinates for the Synthesis of Sulfonylated Pyrrolidones.
Org. Lett. 2019, 21, 2890–2893.
ACS Paragon Plus Environment

Page 23 of 23
The Journal of Organic Chemistry
1
2
3
4
5
(22) Zhou, X.; Luo, J.; Liu, J.; Peng, S.; Deng, G.-J. Pd-Catalyzed Desulfitative Heck Coupling
with Dioxygen as the Terminal Oxidant. Org. Lett. 2011, 13, 1432–1435.
6
7
(23) Liu, Y.; Wang, Q.-L.; Chen, Z.; Zhou, Q.; Li, H.; Zhou, C.-S.; Xiong, B.-Q.; Zhang, P.-L.;
8
9
Tang,
K.-W.
Visible-Light-Catalyzed
with Sulfonyl
C−C
Bond
Difunctionalization
the Synthesis
of
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Methylenecyclopropanes
Chlorides
for
of
3-Sulfonyl-1,2-dihydronaphthalenes. J. Org. Chem. 2019, 84, 2829−2839.
ACS Paragon Plus Environment