Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors

Article abstract of DOI:10.1021/acs.joc.8b03046

Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.

Full text of DOI:10.1021/acs.joc.8b03046

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Article
Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
Zhiguo Zhang, Songnan Wang, Yong Zhang, and Guisheng Zhang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b03046 • Publication Date (Web): 11 Mar 2019
Downloaded from http://pubs.acs.org on March 11, 2019
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Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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Zhiguo Zhang,* Songnan Wang, Yong Zhang, and Guisheng Zhang*
Henan Key Laboratory of Organic Functional Molecule and Drug Innovation, Collaborative Innovation Center of
Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and
Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University,
Xinxiang, Henan 453007, China.
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E-mail: zhangzg@htu.edu.cn and zgs6668@yahoo.com Fax: (+86)-373-332-5250.
Abstract: Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as
all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient
sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the
sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to
couple various inactivated arenes to prepare sulfones at ambient temperature.
Keywords: sulfonyl azides; S-N bond cleavage; arylsulfonyl compounds; cross-coupling; sulfonation;
sulfones
INTRODUCTION
Sulfonyl azides are very important organic compounds that are widely used as sulfonamido group
donors,1 diazo group donors,2 and all-nitrogen 1,3-dipoles donors in [3+2] cycloaddition reactions
leading to 1,2,3-triazoles,3 as well as azide group sources4 in organic synthetic chemistry (Scheme 1).
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However, there are few reports5 where the sulfonyl azides were sulfonyl donors in sulfonylation
reactions via highly selective S-N bond cleavage reactions. In 2010, Lovely and co-workers5a found
that a tosyl derivative was the only substitution product when they treated a methylimidazole derivative
n
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with BuLi and TsN3 in one step of the total synthesis of Naamidine H natural product. Harsh
conditions such as a strong base (nBuLi) and low temperatures (–78 °C) were used, and a large amount
of starting material was recovered. The authors reported: “This was a somewhat surprising result since
we and others have used this approach for the azidation of imidazole C2 position”.5a However, it is
unfortunate that no systematic expansion of this strategy to other aromatic compounds has been
reported (Eq. 1). Very recently, Lam et al.5b reported the generation of sulfonyl radicals from sulfonyl
azides using visible light and a photoactive iridium complex in tetrahydrofuran (THF), which were
used to promote sulfonylative and azido sulfonylative cyclizations of enynes to give several classes of
highly functionalized oxacycles and azacycles. It is noteworthy that the alkyne moiety of the enyne
reagents served as the acceptor of the sulfonyl radicals, whereas the arenes have not been explored in
the conversion (Eq. 2). Thus, the development of a new, mild, and regiospecific S-N bond cleavage
reaction of the sulfonyl azides for incorporating a sulfonyl group into simple arenes, which extends
beyond traditional sulfonylation method, remains unexplored. Therefore, a trifluoromethanesulfonic
acid (TfOH)-promoted Friedel–Crafts type sulfonylation reaction was performed here for rapid access
to a series of sulfone derivatives, with inactivated arenes serving as the electrophilic receptor and the
sulfonyl azides serving as the sulfonyl group donor, via a regiospecific S-N bond cleavage reaction at
ambient temperature (AT) (Scheme 2).
Scheme 1. Versatile building blocks of sulfonyl azides.
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To date, various sulfonyl-containing organic/inorganic compounds including sulfonyl chlorides,6
sulfonic acids,7 sulfonic anhydrides,8 sulphonate,9 sulfonamides,10 sulfohydrazide,11
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dimethylsulfoxide (DMSO),12 DABSO,13 K2S2O8,14 SO2 , and SO3,16 deliver their sulfonyl moiety to
an electrophilic receptor. They then produced sulfone derivatives in the presence of a metal-catalyst
or under metal-free oxidation reactions.17 In addition, oxidation of the sulfides can also be used to
derive sulfones.18 Despite these effective methods, the development of a new environmentally benign
sulfonylation reagent under simple and mild reaction conditions remains a highly desirable,
challenging goal. Sulfonyl azides 1 can react with a strong acid to produce hydrogen azide (HN3) and
a reactive sulfonyl cation might be involved. Accordingly, the sulfonyl cation generated in situ may be
quickly captured by an arene electrophilic receptor, which would produce an arylsulfonyl compound.
RESULTS AND DISCUSSION
From the synthesis of N-containing heterocycles in the presence of brønsted acid,19 the reaction
conditions were optimized for the sulfonyl delivery reaction of 4-methylbenzenesulfonyl azide (1a)
with benzene (2a). Treatment of starting materials 1a (1.0 equiv.) and 2a (1.2 equiv.) with
trifluoromethanesulfonic acid (TfOH, 3 equiv) in dichloromethane (DCM, 0.5 mL) at ambient
temperature produced the desired 1-methyl-4-(phenylsulfonyl)benzene (3a) as a white solid in a 92%
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yield after 3 h. The structure of 3a was identified with H NMR, C NMR, high-resolution mass
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spectrometry (HRMS), and MS (Table 1, entry 1). However, a lower yield of 3a along with recovered
1a was obtained if the amount of TfOH was decreased (Table 1, entries 2 and 3). Other brønsted acids
including methanesulfonic acid (MSA), 4-methylbenzenesulfonic acid (TsOH), H2SO4, HNO3, and
AcOH were ineffective for the reaction (Table 1, entries 4–8). Further investigation of this
intermolecular cross-coupling reaction with different solvents indicated that 1,4-dioxane, THF,
methanol, diethyl ether, and DMSO did not yield the desired compound 3a (Table 1, entries 9–13).
Table 1. Survey of the reaction conditions.a
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Entry
Acid (equiv)
TfOH (3.0)
TfOH (2.0)
TfOH (1.0)
MSA (3.0)
TsOH (3.0)
H2SO4 (3.0)
HNO3 (3.0)
AcOH (3.0)
TfOH (3.0)
TfOH (3.0)
Solvent
DCM
Time/h
Yield of 3a/% Recovered 1a/%
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92
0
DCM
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97
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DCM
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DCM
NR
NR
NR
NR
NR
NR
NR
DCM
DCM
DCM
DCM
1,4-Dioxane
THF
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TfOH (3.0)
TfOH (3.0)
TfOH (3.0)
Methanol
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NR
NR
8
96
95
85
Diethyl ether
DMSO
a Unless otherwise indicated, all reactions were carried out with 1a (1.0 mmol), 2a (1.2 equiv) in
0.5 mL anhydrous solvents at ambient temperature.
Under optimized conditions (Table 1, entry 1), the scope of this Friedel–Crafts type sulfonylation
reaction was examined (Scheme 2). Various sulfonyl azides (1) with different aryl groups (R1) were
investigated first. The starting materials 1a–c bearing the methyl group (-Me) at the ortho-, meta-, and
para-positions, 1d with a methoxyl group (-OMe) at the para-position, and benzenesulfonyl azide (1e)
smoothly reacted with benzene (2a), and yielded (84%–92%) the desired sulfones 2a–e at ambient
temperatures. Naphthalene-2-sulfonyl azide (1f) under the same conditions coupled with 2a to achieve
an excellent yield of 3f (97%). When para-chloro and para-trifluoromethyl-substituted
benzenesulfonyl azides 1g and 1h were employed as substrates, the corresponding sulfonylated
products 3g (90%) and 3h (97%) were obtained exclusively. Furthermore, the arylsulfonyl azides 1i
and 1j with electron withdrawing groups, including -CO2Et or -NO2 groups at the para-position of the
benzene ring, were used for the sulfonylation reaction, and yielded sulfonylated products 3i and 3j (83%
and 94%, respectively) at 60 °C. This type of diaryl sulfone derivative generally cannot be synthesized
with sulfonylation reagents and arenes bearing the EWG(s) on the aryl ring because of limitations of
the Friedel–Crafts reaction. These results thus indicated the practicality and flexibility of the present
strategy.
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Scheme 2. Extension of the reaction scope a
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3a: 3 h, 92%
3e: 3 h, 86%
3c: 3 h, 92%
3b: 3 h, 91%
3f: 3 h, 97%
3d: 3 h, 84%
3h: 24 h, 97%
3l: 5 h, 98%b
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3g: 3 h, 90%
3k: 5 h, NRc
O
O
S
O2N
3i: 5 h, 83%b
3j: 24 h, 94%b
O
O
S
S
3m: 3 h, 89%
3o: 3 h, 80%
3s: 5 h, 75%
3p: 3 h, 67%e
3n: 5 h, 45%d
3r: 3 h, 59%g
3q: 3 h, 78%f
3t: 5 h, 93%
3x: 3 h, 99%
3w: 3 h, 58%
3u: 3 h, 95%h
3v: 5 h, 91%i
3z: 3 h, 93%
3y: 3 h, 81%
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a
Unless otherwise indicated, all reactions were carried out with 1 (1.0 mmol), 2 (1.2 equiv), and
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TfOH (3.0 equiv) in anhydrous DCM (0.5 mL) at ambient temperature.
b Reaction was performed at 60 °C.
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c 85% of 1k was recovered.
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d 2.4 equiv of 2a was used.
e 30% of ortho-sulfonylated product 1-methoxy-2-tosylbenzene (3p’) was obtained.
f 9% of ortho-sulfonylated product 1-methyl-2-tosylbenzene (3q’) was obtained.
g 37% of α-sulfonylated product 1-tosylnaphthalene 3r’ was obtained.
h 3.0 equiv of 1a was used.
i 5.0 equiv of 1a was used.
The extension of the reaction scope revealed that compound 1k was not a viable substrate for the
reaction for sulfone 3k formation, even at 60 °C. In contrast, starting material 1l with a weak basic
amide group on the benzene yielded the sulfonylated product 3l (98%) at 60 °C. These observations
indicated that it was largely caused by a salt-forming reaction of alkaline pyridine (1k) with the strong
acid TfOH. Moreover, thiophene-2-sulfonyl azide (1m) also reacted smoothly with 2a to give the
desired product 3m in an 89% yield. Benzene-1,2-disulfonyl diazide (1n) could also be subjected to
the sulfonylation reaction to give the desired product 3n in a 45% yield, regardless of steric hindrance.
The source of the sulfonyl moiety was not limited to an arylsulfonyl group. n-Butyl-substituted
sulfonyl azide 1o could also be applied as a sulfonyl donor, and the sulfonylation reaction between 1o
and 2a proceeded smoothly at ambient temperature to produce target compound 3o in a 80% isolated
yield.
Various arenes were tried for reaction with 1a. Beyond benzene (2a) used for 3a–o, other substituted
benzenes, including anisole (2b), toluene (2c), naphthalene (2d), 1,2-dichlorobenzene (2e), and
bromobenzene (2f) were viable substrates. However, in the cases of 2b–d, they produced not only
para-sulfonylated products 3p–t (37%–93%), but also an ortho-substituted isomer 3p–r. In addition,
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biphenyl (2g) and triphenylmethane (2h) worked as well; the corresponding di- and trisulfonylated
products 3p and 3q were isolated in 95% and 91% yields, respectively. 5-tosylindolin-2-one (3w) was
obtained in a 58% yield when 1a reacted with benzoheterocyclic compound indolin-2-one (2i). In
conjunction with the product 3l, this selectable bond-formation reaction demonstrated the practicality
and flexibility of the protocol. The sulfonylation strategy could occur not only in an intermolecular
reaction, but also in an intramolecular reaction. The sulfonylation of [1,1’-biphenyl]-2-sulfonyl azide
(1x) was also feasible, resulting in an almost quantitative yield of 3x (99%) via an intramolecular
annulation reaction. Starting material m-xylene also proceed well with 1a. The cross-coupling reaction
occurred specifically at the para-position of the methyl of m-xylene, gave the desired product 3z in
93% yield after 3 h under optimized conditions. We also reacted some heterocycles starting materials
with 1a, including indole, benzo[d]oxazole, 1H-benzo[d]imidazole, and benzofuran. They did not
afford the desired products 3. Some unidentified complex mixture was observed in the case of indole
and benzofuran. Some starting materials was recovered in the case of benzo[d]oxazole and 1H-
benzo[d]imidazole.
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The sulfonyl group is an important moiety that frequently appears in biological molecules,
pharmaceuticals, pesticides, and polymers. They distinctly enhance certain features, such as
benzobicylon, thiamphemcol, and HDACI.20 It can also serve as a protecting group for functional
groups,21 or a “baton” that adds to and then leaves from an intermediate in organic synthetic reactions.5a,
22 These benefits contribute to the diversity of their synthetic methods. With this strategy, the reaction
of 1g with chlorobenzene could be easily performed at ambient temperature affording 3y in 81% yield
after 3 h. This valuable molecule (3y) now is a commercial reagent and could be used for the synthesis
of poly(oxy-1,4-phenylenesulfonyl-1,4-phenylene),23 Acedapsone,24 Dapsone,14 and other useful
valuable derivatives14 via a simple derivatization reaction (Scheme 3). Acedapsone and Dapsone are
antibiotics commonly used in combination with rifampicin and clofazimine for the treatment of leprosy,
acne,25 dermatitis herpetiformis, and various other skin conditions.26 To further demonstrate the
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practicality of the reaction, a large-scale synthesis was examined. For example, the reactions of 1a (1.2
g, 6 mmol) with 2a (7.2 mmol) were conducted. It gave 3a (1.342 g) in 97% yield after 18 h.
Scheme 3. Representative sulfonyl-containing molecules.
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From the experimental results and proposed mechanisms reported elsewhere,10a, 27 a probable
pathway for the Friedel–Crafts-type cross-coupling of inactivated arenes and sulfonyl azides to prepare
diaryl sulfone derivatives is given in Scheme 4. Initially, the acylation donor sulfonyl azides 1 reacted
with TfOH to produce hydrogen azide (HN3) and the sulfonyl cation A with TfO– anion as the
counterion. This is a potential agent for the Friedel–Crafts sulfonylation. Subsequently, the arene was
activated by the electrophilic sulfonyl cation A to form the desired sulfonylation product 2 by
deprotonation.28b,29
Scheme 4. Proposed mechanism.
■ CONCLUSION
In summary, a trifluoromethanesulfonic acid (TfOH)-promoted regiospecific N-S bond cleavage
reaction of sulfonyl azides was developed. It coupled with various inactivated arenes and led to a series
of sulfones in good to excellent yields at ambient temperature via Friedel–Crafts type cross-coupling
reactions. The procedure was very different from previous aromatic sulfonation reactions performed
with sulfonyl chlorides, sulfonic acids, sulphonate, and sulfohydrazide. Here, the cross-coupling
method proceeded with readily available sulfonyl azides, without high temperature, additives, metal
catalysts, and or complex execution. More importantly, the sulfonyl azides served as a donor of
sulfonyl groups, rather than a sulfonamido group donor, a diazo group donor, an all-nitrogen 1,3-
dipoles donor, and an azide group source. This will largely broaden application ranges. Furthermore,
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the synthetic potential of the products makes this novel intramolecular cyclization very attractive.
Application of this Friedel–Crafts sulfonylation to other systems, especially other heterocycles, is
currently under investigation.
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■ EXPERIMENTAL SECTION
o
General Remarks. All reactions were carried out at 25 C, unless otherwise indicated. All other
reagents were purchased from commercial sources and used without further treatment, unless
otherwise indicated. Starting materials 1 was synthesized following the known literatures.30 Petroleum
o
ether (PE) used here refers to the 60-90 C boiling point fraction of petroleum. Ethyl acetate is
1
13
abbreviated as EA. H and C{1H} NMR spectra were recorded on a Bruker Avance/600 (1H: 600
MHz, 13C{1H}: 150 MHz at 25 ºC) or Bruker Avance/400 (1H: 400 MHz, 13C{1H}: 100 MHz at 25 ºC)
with tetramethylsilane as the internal standard. Data are represented as follows: chemical shift,
integration, multiplicity (br = broad, s = singlet, d = doublet, dd = double doublet, t = triplet, q = quartet,
and m = multiplet), and coupling constants in Hertz (Hz). All high-resolution mass spectra (HRMS)
were measured on a mass spectrometer by using electrospray ionization orthogonal acceleration time-
1
of-flight (ESI-oa-TOF), and the purity of all samples used for HRMS (>95%) was confirmed by H
and 13C{1H} NMR spectroscopic analysis. Melting points were measured on a melting point apparatus
equipped with a thermometer and were uncorrected. All reactions were monitored by thin-layer
chromatography (TLC) with GF254 silica gel-coated plates, and in general, it was designated as the
end of the reaction when the starting material 1 was consumed 1 h later. Flash chromatography was
carried out on SiO2 (silica gel 200−300 mesh).
The general procedure for the synthesis of 3 (3a as example): In a round-bottomed flask (25 mL)
equipped with a magnetic stirrer, a solution of CH2Cl2 (0.5 mL) and benzenesulfonyl azide (1a) (183
mg, 1.0 mmol) was prepared. Benzene (2a) (0.107 mL, 1.2 mmol) was added to the solution and the
reaction mixture was stirred magnetically. Then TfOH (0.25 mL, 3.0 mmol) was added. The mixture
was well-stirred for 3 h at ambient temperature. After complete conversion, as indicated by thin-layer
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chromatography, the reaction was quenched by water and extracted with dichloromethane (3 × 5 mL).
The combined filtrate was washed with saturated brine (2 × 5 mL), and dried over anhydrous Mg2SO4.
The residue was purified by column chromatography on a silica gel with ethyl acetate: petroleum ether
(2:45) to provide the desired product 3a as a white solid (213 mg, 92%).
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1-Methyl-4-(phenylsulfonyl)benzene (3a).31 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (214 mg, 92%): mp: 123-124 oC; 1H NMR (600 MHz, CDCl3)
δ 7.93 (d, J = 7.8 Hz, 2H), 7.83 (d, J = 7.2 Hz, 2H), 7.54 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.5 Hz, 2H),
7.30 (d, J = 7.8 Hz, 2H), 2.40 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 144.1, 142.0, 138.7, 133.0, 129.9,
129.2, 127.7, 127.5, 21.6. HRMS (ESI), m/z calcd. for C13H13O2S ([M+H]+) 233.0631, found:
233.0630.
1-Methyl-3-(phenylsulfonyl)benzene (3b).31 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (212 mg, 91%): mp: 119-120 oC; 1H NMR (600 MHz, CDCl3)
δ 7.94 (d, J = 7.2 Hz, 2H), 7.75 (d, J = 7.8 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.5 Hz, 2H),
7.38 (dd, J = 18.0, 7.8, 2H), 2.40 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 141.8, 141.4, 139.5, 134.0,
133.1, 129.2, 129.1, 127.9, 127.6, 124.8, 21.3. HRMS (ESI), m/z calcd. for C13H12NaO2S ([M+Na]+)
255.0450, found: 255.0450.
1-Methyl-2-(phenylsulfonyl)benzene (3c).31 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (214 mg, 92%): mp: 79-81 oC; 1H NMR (600 MHz, CDCl3) δ
8.22 (d, J = 7.8 Hz, 1H), 7.87 (d, J = 7.8 Hz, 2H), 7.57 (t, J = 6.9 Hz, 1H), 7.49 (dd, J = 16.8, 8.4 Hz,
3H), 7.40 (t, J = 7.5 Hz, 1H), 7.23 (d, J = 7.2 Hz, 1H), 2.44 (s, 3H). 13C NMR (150 MHz, CDCl3) δ
141.3, 138.8, 138.0, 133.6, 133.0, 132.7, 129.4, 129.0, 127.7, 126.5, 20.2. HRMS (ESI), m/z calcd. for
C13H12NaO2S ([M+Na]+) 255.0450, found: 255.0449.
1-Methoxy-4-(phenylsulfonyl)benzene (3d).31 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (209 mg, 84%); mp: 91-93 oC; 1H NMR (600 MHz, CDCl3) δ
7.91 (d, J = 7.2 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.53 (t, J = 6.9 Hz, 1H), 7.48 (t, J = 7.2 Hz, 2H),
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6.96 (d, J = 8.4 Hz, 2H), 3.84 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 163.4, 142.4, 133.1, 132.8, 129.9,
129.2, 127.3, 114.5, 55.6. HRMS (ESI), m/z calcd. for C13H13O3S ([M+H]+) 249.0580, found:
249.0580.
Sulfonyldibenzene (3e).31 The product was isolated by flash chromatography (eluent: EA/PE = 1/22)
as a white solid (187 mg, 86%): mp: 119-121 oC; 1H NMR (600 MHz, CDCl3) δ 7.95 (d, J = 7.8 Hz,
4H), 7.56 (t, J = 7.2 Hz, 2H), 7.50 (t, J = 7.5 Hz, 4H). 13C NMR (150 MHz, CDCl3) δ 141.6, 133.2,
129.3, 127.7. HRMS (ESI), m/z calcd. for C12H10NaO2S ([M+Na]+) 241.0294, found: 241.0294.
2-(Phenylsulfonyl)naphthalene (3f).31 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a yellow solid (260 mg, 97%): mp: 120-122 oC; 1H NMR (400 MHz, CDCl3) δ 8.58
(s, 1H), 7.99 (t, J = 7.8 Hz, 3H), 7.93 (d, J = 8.8 Hz, 1H), 7.86 (t, J = 8.2 Hz, 2H), 7.67-7.58 (m, 2H),
7.56 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.4 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 141.7, 138.4, 135.0,
133.2, 132.2, 129.6, 129.4, 129.3, 129.1, 129.09, 127.9, 127.7, 127.6, 122.7. HRMS (ESI), m/z calcd.
for C16H13O2S ([M+H]+) 269.0631, found: 269.0631.
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1-Chloro-4-(phenylsulfonyl)benzene (3g).32 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (227 mg, 90%): mp: 93-94 oC; 1H NMR (600 MHz, CDCl3) δ
7.93 (d, J = 7.8 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H),
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7.47 (d, J = 8.4 Hz, 2H). C NMR (150 MHz, CDCl3) δ 141.2, 140.1, 139.9, 133.4, 129.6, 129.4,
129.1, 127.6. HRMS (ESI), m/z calcd. for C12H9ClNaO2S ([M+Na]+) 274.9904, found: 274.9908.
1-(Phenylsulfonyl)-4-(trifluoromethyl)benzene (3h).31 The product was isolated by flash
chromatography (eluent: EA/PE = 1/22) as a brown solid (277 mg, 97%): mp: 87-88 oC; 1H NMR (400
MHz, CDCl3) δ 8.07 (d, J = 8.4 Hz, 2H), 7.96 (d, J = 7.2 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.61 (t, J
= 7.4 Hz, 1H), 7.54 (t, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 145.3, 140.6, 134.9 (d, J = 32.9
Hz), 133.8, 129.6, 128.2, 127.9, 126.5 (q, J = 3.7 Hz), 123.11 (d, J = 271.4 Hz). 19F NMR (565 MHz,
CDCl3) δ -63.2. HRMS (ESI), m/z calcd. for C13H9F3NaO2S ([M+Na]+) 309.0168, found: 309.0168.
Ethyl 4-(phenylsulfonyl)benzoate (3i).34 The product was isolated by flash chromatography (eluent:
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EA/PE = 1/22) as a yellow oil (242 mg, 83%); 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.4 Hz, 2H),
8.00 (d, J = 8.8 Hz, 2H), 7.94 (d, J = 7.6 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H),
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4.38 (dd, J = 14.0 Hz,7.2 Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H). C NMR (100 MHz, CDCl3) δ 165.0,
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145.4, 140.9, 134.7, 133.6, 130.4, 129.5, 127.8, 127.7, 61.7, 14.2. HRMS (ESI), m/z calcd. for
C15H14NaO4S ([M+Na]+) 313.0505, found: 313.0499.
1-Nitro-4-(phenylsulfonyl)benzene (3j).32 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a yellow solid (247 mg, 94%): mp: 141-142 oC; 1H NMR (600 MHz, CDCl3)
δ 8.34 (d, J = 8.4 Hz, 2H), 8.13 (d, J = 8.4 Hz, 2H), 7.97 (d, J = 7.2 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H),
7.56 (t, J = 7.5 Hz, 2H). 13C NMR (150 MHz, CDCl3) δ 150.3, 147.4, 140.0, 134.1, 129.7, 129.0, 128.0,
124.5. HRMS (ESI), m/z calcd. for C12H9NNaO4S ([M+Na]+) 286.0144, found: 286.0142.
N-(4-(phenylsulfonyl)phenyl)acetamide (3l).31 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a white solid (270 mg, 98%): mp: 180-182 oC; 1H NMR (600 MHz, CDCl3)
δ 7.90 (d, J = 6.6 Hz, 2H), 7.84 (d, J = 7.2 Hz, 2H), 7.81 (s, 1H), 7.65 (d, J = 7.8 Hz, 2H), 7.55 (t, J =
7.2 Hz, 1H), 7.49 (t, J = 6.9 Hz, 2H), 2.17 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 168.9, 142.6, 141.7,
135.9, 133.2, 129.3, 129.0, 127.4, 119.6, 24.7. HRMS (ESI), m/z calcd. for C14H13NNaO3S ([M+Na]+)
298.0508, found: 298.0510.
2-(Phenylsulfonyl)thiophene (3m).32 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (200 mg, 89%): mp: 116-118 oC; 1H NMR (600 MHz, CDCl3) δ 7.99
(d, J = 7.2 Hz, 2H), 7.70 (dd, J = 3.6 Hz, 1H), 7.64 (dd, J = 4.8 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.52
(t, J = 7.5 Hz, 2H), 7.08 (dd, J = 4.8, 4.2 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 143.1, 142.1, 133.9,
133.4, 133.3, 129.3, 127.8, 127.3. HRMS (ESI), m/z calcd. for C10H9O2S2 ([M+H]+) 225.0038, found:
225.0037.
1,2-Bis(phenylsulfonyl)benzene (3n).37 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a yellow solid (161 mg, 45%): mp: 109-110 oC; 1H NMR (600 MHz, CDCl3) δ 8.49
(t, J = 3.9 Hz, 2H), 7.97 (d, J = 7.8 Hz, 4H), 7.84 (t, J = 3.9 Hz, 2H), 7.58 (t, J = 7.2 Hz, 2H), 7.51 (t,
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J = 7.5 Hz, 4H). 13C NMR (150 MHz, CDCl3) δ 141.5, 140.3, 133.9, 133.3, 128.7, 128.0. HRMS (ESI),
m/z calcd. for C18H14NaO4S2 ([M+Na]+) 381.0226, found: 381.0235.
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(Butylsulfonyl)benzene (3o).38 The product was isolated by flash chromatography (eluent: EA/PE
= 1/22) as a yellow oil (159 mg, 80%); 1H NMR (600 MHz, CDCl3) δ 7.91 (d, J = 7.8 Hz, 2H), 7.65
(t, J = 7.2 Hz, 1H), 7.57 (t, J = 7.8 Hz, 2H), 3.08 (t, J = 7.8 Hz, 2H), 1.73-1.65 (m, 2H), 1.39 (m, 2H),
0.89 (t, J = 7.5 Hz, 3H). 13C NMR (150 MHz, CDCl3) δ 139.2, 133.6, 129.2, 128.0, 56.1, 24.6, 21.5,
13.5. HRMS (ESI), m/z calcd. for C10H14NaO2S ([M+Na]+) 221.0607, found: 221.0606.
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1-Methoxy-4-tosylbenzene (3p).34 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (176 mg, 67%): mp: 157-158 oC; 1H NMR (600 MHz, CDCl3) δ 7.86
(d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.2 Hz, 2H), 7.27 (d, J = 7.8 Hz, 2H), 6.95 (d, J = 7.2 Hz, 2H), 3.83
(s, 3H), 2.38 (s, 3H).13C NMR (150 MHz, CDCl3) δ 163.1, 156.3, 143.7, 133.8, 129.8, 129.7, 127.4,
114.4, 55.6, 21.5. HRMS (ESI), m/z calcd. for C14H14NaO3S ([M+Na]+) 285.0556, found: 285.0563.
1-Methoxy-2-tosylbenzene (3p’).39 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (79 mg, 30%): mp: 105-107 oC; 1H NMR (600 MHz, CDCl3) δ 8.14
(d, J = 7.8 Hz, 1H), 7.85 (d, J = 7.8 Hz, 2H), 7.52 (t, J = 7.8 Hz, 1H), 7.27 (d, J = 7.8 Hz, 2H), 7.09 (t,
J = 7.5 Hz, 1H), 6.89 (d, J = 7.8 Hz, 1H), 3.77 (s, 3H), 2.41 (s, 3H). 13C NMR (150 MHz, CDCl3) δ
157.0, 143.7, 138.6, 135.3, 129.8, 129.3, 129.1, 128.5, 120.5, 112.4, 55.8, 21.6. HRMS (ESI), m/z
calcd. for C14H14NaO3S ([M+Na]+) 285.0556, found: 285.0562.
4,4’-Sulfonylbis(methylbenzene) (3q).33 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (192 mg, 78%): mp: 157-158 oC; 1H NMR (600 MHz, CDCl3) δ 7.81
(d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 143.9, 139.1,
129.9, 127.7, 21.5. HRMS (ESI), m/z calcd. for C14H14NaO2S ([M+Na]+) 269.0607, found: 269.0615.
1-Methyl-2-tosylbenzene (3q’).34 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white oil (22 mg, 9%); 1H NMR (600 MHz, CDCl3) δ 8.19 (d, J = 7.8 Hz, 1H),
7.74 (d, J = 7.8 Hz, 2H), 7.46 (t, J = 7.2 Hz, 1H), 7.38 (t, J = 7.8 Hz, 1H), 7.29 (d, J = 7.8 Hz, 2H),
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7.22 (d, J = 7.2 Hz, 1H), 2.44 (s, 3H), 2.40 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 143.95, 139.20,
138.33, 137.89, 133.44, 132.62, 129.65, 129.29, 127.77, 126.42, 21.58, 20.20. HRMS (ESI), m/z
calcd. for C14H14NaO2S ([M+Na]+) 269.0607, found: 269.0613.
Mixture of 2-Tosylnaphthalene (3r) and 1-Tosylnaphthalene (3r’).35 The product was isolated by
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flash chromatography (eluent: EA/PE = 1/22) as a pink solid (272 mg, 96%); H NMR (600 MHz,
CDCl3) δ 8.64 (d, J = 8.4 Hz, 1H), 8.56 (s, 1H), 8.49 (d, J = 7.2 Hz, 1H), 8.08 (d, J = 8.4 Hz, 1H), 7.97
(d, J = 7.8 Hz, 1H), 7.83-7.98 (m, 7H), 7.66-7.57 (m, 3H), 7.53 (t, J = 7.2 Hz, 1H), 7.29 (d, J = 7.2 Hz,
2H), 7.25 (s, 1H), 2.38 (s, 3H), 2.36 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 144.2, 144.0, 138.9, 138.7,
136.2, 135.0, 134.2, 129.9, 129.8, 129.6, 129.4, 129.0, 129.0, 128.8, 128.5, 128.3, 127.9, 127.8, 127.6,
127.5, 126.8, 124.4, 124.4, 122.7, 21.5. HRMS (ESI), m/z calcd. for C17H14NaO2S ([M+Na]+)
305.0607, found: 305.0604.
1,2-Dichloro-4-tosylbenzene (3s).36 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (224 mg, 75%): mp: 252-255 oC; 1H NMR (600 MHz, CDCl3) δ 8.00
(s, 1H), 7.81 (d, J = 7.2 Hz, 2H), 7.74 (d, J = 7.8 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 7.2 Hz,
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2H), 2.42 (s, 3H). C NMR (150 MHz, CDCl3) δ 144.9, 141.9, 138.0, 137.7, 133.9, 131.3, 130.2,
129.4, 127.8, 126.5, 21.6. HRMS (ESI), m/z calcd. for C13H10Cl2NaO2S ([M+Na]+) 322.9671, found:
322.9676.
1-Bromo-4-tosylbenzene (3t).33 The product was isolated by flash chromatography (eluent: EA/PE
= 1/22) as a white solid (288 mg, 93%): mp: 135-136 oC; 1H NMR (600 MHz, CDCl3) δ 7.79 (dd, J =
12.9, 8.1 Hz, 4H), 7.62 (d, J = 7.8 Hz, 2H), 7.30 (d, J = 7.8 Hz, 2H), 2.40 (s, 3H). 13C NMR (150 MHz,
CDCl3) δ 144.5, 141.1, 138.2, 132.5, 130.0, 129.0, 128.2, 127.7, 21.6. HRMS (ESI), m/z calcd. for
C13H11BrNaO2S ([M+Na]+) 332.9555, found: 332.9551.
4,4'-Ditosyl-1,1'-biphenyl (3u). The product was isolated by flash chromatography (eluent: EA/PE
= 1/5) as a yellow solid (439 mg, 95%): mp: >300 oC; 1H NMR (600 MHz, CDCl3) δ 8.00 (d, J = 8.4
Hz, 2H), 7.85 (d, J = 7.8 Hz, 2H), 7.64 (d, J = 7.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 2.40 (s, 3H). 13C
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NMR (150 MHz, CDCl3) δ 144.5, 143.9, 141.9, 138.4, 130.1, 128.3, 128.2, 127.8, 21.6. HRMS (ESI),
m/z calcd. for C26H23O4S2 ([M+H]+) 463.1032, found: 463.1041.
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Tris(4-tosylphenyl)methane (3v). The product was isolated by flash chromatography (eluent:
EA/PE = 1/2) as a yellow solid (643 mg, 91%): mp: 75-77 oC; 1H NMR (600 MHz, CDCl3) δ 7.81 (dd,
J = 12.9, 8.1 Hz, 12H), 7.30 (d, J = 7.2 Hz, 6H), 7.10 (d, J = 7.2 Hz, 6H), 5.57 (s, 1H), 2.40 (s, 9H).
13C NMR (150 MHz, CDCl3) δ 146.6, 144.5, 141.2, 138.3, 130.1, 130.0, 128.0, 127.8, 56.1, 21.6.
HRMS (ESI), m/z calcd. for C40H34NaO6S3 ([M+Na]+) 729.1410, found: 729.1416.
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5-Tosylindolin-2-one (3w). The product was isolated by flash chromatography (eluent: EA/PE =
1/22) as a yellow solid (167 mg, 58%): mp: 250-253 oC; 1H NMR (400 MHz, DMSO) δ 10.81 (s, 1H),
7.78 (d, J = 8.4 Hz, 3H), 7.71 (s, 1H), 7.40 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.0 Hz, 1H), 3.56 (s, 2H),
2.36 (s, 3H). 13C NMR (100 MHz, DMSO) δ 176.4, 148.5, 143.8, 139.2, 133.6, 130.0, 128.1, 127.3,
127.0, 123.3, 109.3, 35.5, 20.9. HRMS (ESI), m/z calcd. for C15H13NNaO3S ([M+Na]+) 310.0508,
found: 310.0521.
Dibenzo[b,d]thiophene 5,5-dioxide (3x).40 The product was isolated by flash chromatography
(eluent: EA/PE = 1/22) as a yellow solid (214 mg, 99%): mp: 182-183 oC; 1H NMR (400 MHz, CDCl3)
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δ 7.82 (dd, J = 11.6, 7.6 Hz, 2H), 7.65 (td, J = 7.6, 1.1 Hz, 1H), 7.54 (td, J = 7.6, 0.8 Hz, 1H). C
NMR (100 MHz, CDCl3) δ 137.8, 133.9, 131.6, 130.4, 122.2, 121.6. HRMS (ESI), m/z calcd. for
C12H9O2S ([M+H]+) 217.0318, found: 217.0325.
4,4’-Sulfonylbis(chlorobenzene) (3y).41 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a white solid (232 mg, 81%): mp: 143-146 oC; 1H NMR (600 MHz, CDCl3) δ 7.86
(d, J = 8.4 Hz, 4H), 7.49 (d, J = 8.4 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ 140.2, 139.8, 129.8, 129.1.
HRMS (ESI), m/z calcd. for C12H8Cl2NaO2S ([M+Na]+) 308.9514, found: 308.9511.
1,3-Dimethyl-5-tosylbenzene (3z).42 The product was isolated by flash chromatography (eluent:
EA/PE = 1/22) as a yellow oil (242 mg, 93%); 1H NMR (600 MHz, CDCl3) δ 8.07 (d, J = 8.4 Hz, 1H),
7.72 (d, J = 7.8 Hz, 2H), 7.27 (d, J = 8.4 Hz, 2H), 7.17 (d, J = 7.8 Hz, 1H), 7.02 (s, 1H), 2.39 (s, 6H),
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2.35 (s, 3H). C NMR (150 MHz, CDCl3) δ 144.2, 143.7, 138.7, 137.7, 136.2, 133.3, 129.5, 129.5,
127.6, 127.0, 21.5, 21.3, 20.1. HRMS (ESI), m/z calcd. for C15H17O2S ([M+H]+) 260.0944, found:
260.0956.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:
Screening of reaction conditions and NMR spectra for compounds (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: zhangzg@htu.edu.cn.
*E-mail: zgs6668@yahoo.com
ACKNOWLEDGMENTS
We thank the NSFC (U1604285, 21272057, 2121772032 and 21702051), PCSIRT (IRT1061), the
111 Project (D17007), Henan Provincial Natural Science Foundation (162300410180), Science &
Technology Innovation Talents in Universities of Henan Province (17HASTIT002), Program for
Innovative Research Team of Science and Technology in the University of Henan Province
(18IRTSTHN004), and Outstanding Young Talent Cultivation Project Funding of Henan Normal
University (14YR002).
References
(1) Pal, K.; Volla, C. M. R. Rhodium-catalyzed denitrogenative transannulation of 1,2,3-triazolyl-
carbamates: Efficient access to 4-aminooxazolidinones. Org. Chem. Front. 2017, 4, 1380.
(2) Hewitt, W. M.; Egger, M.; Zuckerman, N. B.; Konopelski, J. P. Preparation of fused β-lactams
through Weinreb amide α-anions. Tetrahedron 2014, 70, 5283.
(3) (a) Kim, S. H.; Park, S. H.; Choi, J. H.; Chang, S. Sulfonyl and phosphoryl azides: Going further
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 25
1
2
3
4
5
6
7
8
9
beyond the click realm of alkyl and aryl azides. Chem – Asian. J. 2011, 6, 2618. (b) Hein, J. E.; Fokin,
V. V. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I)
acetylides. Chem. Soc. Rev. 2010, 39, 1302. (c) Liu, Z.; Ji, H.; Gao, W.; Zhu, G.; Tong, L.; Lei, F.;
Tang, B. Copper(I)-mediated carboamination of vinyl azides by aryldiazonium salts: synthesis of N2-
substituted 1,2,3-triazoles. Chem. Commun. 2017, 53, 6259-6262.
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
(4) (a) Lindel, T.; Hochgürtel, M. Synthesis of the marine natural product oroidin and its Z-isomer.
J. Org. Chem. 2000, 65, 2806. (b) Bhandari, M. R.; Sivappa, R.; Lovely, C. J. Total Synthesis of the
Putative Structure of Nagelamide D. Org. Lett. 2009, 11, 1535.
(5) (a) Koswatta, P. B.; Lovely, C. J. Concise total synthesis of Naamine G and Naamidine H. Chem.
Commun. 2010, 46, 2148. (b) Zhu, S.; Pathigoolla, A.; Lowe, G.; Walsh, D. A.; Cooper, M.; Lewis, W.;
Lam, H. W. Sulfonylative and azidosulfonylative cyclizations by visible-light-photosensitization of
sulfonyl azides in THF. Chem – Eur. J. 2017, 23, 17598.
(6) (a) Bandgar, B. P.; Kamble, V. T.; Fulse, D. B.; Deshmukh, M. V. Synthesis of sulfones using
sodium perchlorate as a catalyst under neutral conditions. New J. Chem. 2002, 26, 1105. (b) Xie, L.-
Y.; Li, Y.-J.; Qu, J.; Duan, Y.; Hu, J.; Liu, K.-J.; Cao, Z.; He, W.-M. A base-free, ultrasound accelerated
one-pot synthesis of 2-sulfonylquinolines in water. Green Chem. 2017, 19, 5642.
(7) (a) Olah, G. A.; Mathew, T.; Prakash, G. K. Nafion-H catalysed sulfonylation of aromatics with
arene/alkenesulfonic acids for the preparation of sulfones1a. Chem. Commun. 2001, 1696. (b) Lu, Q.;
Zhang, J.; Wei, F.; Qi, Y.; Wang, H.; Liu, Z.; Lei, A. Aerobic oxysulfonylation of alkenes leading to
secondary and tertiary β-hydroxysulfones. Angew. Chem. Int. Ed. 2013, 52, 7156. (c) Wu, C.; Yang, P.;
Fu, Z.; Peng, Y.; Wang, X.; Zhang, Z.; Liu, F.; Li, W.; Li, Z.; He, W. Regio- and stereoselective
hydrosulfonation of alkynylcarbonyl compounds with sulfinic acid in water. J. Org. Chem. 2016, 81,
ACS Paragon Plus Environment

Page 19 of 25
The Journal of Organic Chemistry
1
2
3
4
5
10664.
6
7
8
9
(8) Répichet, S.; Le Roux, C.; Hernandez, P.; Dubac, J.; Desmurs, J.-R. Bismuth(III)
trifluoromethanesulfonate:ꢀAn efficient catalyst for the sulfonylation of arenes. J. Org. Chem. 1999,
64, 6479.
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
(9) (a) Khodaei, M. M.; Nazari, E. Sulfonylation of aromatic compounds with methyl p-
toluenesulfonate as a sulfonylating precursor. J. Iran. Chem. Soc. 2012, 9, 507. (b) 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. (c) Xie, L.-Y.; Peng, S.; Liu, F.; Chen, G.-R.; Xia, W.; Yu, X.; Li, W.-F.;
Cao, Z.; He, W.-M. Metal-free deoxygenative sulfonylation of quinoline N-oxides with sodium
sulfinates via a dual radical coupling process. Org. Chem. Front. 2018, 5, 2604.
(10) (a) Yao, B.; Zhang, Y. Sulfonylation of arenes with sulfonamides. Tetrahedron Lett. 2008, 49,
5385. (b) Liu, Z.; Chen, X.; Chen, J.; Qu, L.; Xia, Y.; Wu, H.; Ma, H.; Zhu, S.; Zhao, Y. Copper
catalyzed direct tert-butyl sulfonylation of alkynes with t-butylsulfinamide leading to (E)-vinyl
sulfones. Rsc Adv. 2015, 5, 71215.
(11) (a) Wu, X. M.; Wang, Y. A mild and base-free synthesis of unsymmetrical diaryl sulfones from
arylboronic acids and arylsulfonyl hydrazides. Synlett 2014, 25, 1163. (b) Zhang, P.; Gao, Y.; Chen, S.;
Tang, G.; Zhao, Y. Direct synthesis of 2-sulfonated 9H-pyrrolo[1,2-a]indoles via NaI-catalyzed
cascade radical addition/cyclization/isomerization. Org. Chem. Front. 2017, 4, 1350. (c) Li, B.; Li, Y.;
Yu, L.; Wu, X.; Wei, W. Metal-free sulfonylation of quinones with sulfonyl hydrazides in water: Facile
access to mono-sulfonylated hydroquinones. Tetrahedron 2017, 73, 2760. (d) Wang, S.; Huang, X.;
Wang, Q.; Ge, Z.; Wang, X.; Li, R. An efficient synthesis of sulfonated quinoline diones by copper
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 25
1
2
3
4
5
catalyzed sulfonylation of activated alkenes with sulfonylhydrazides. Rsc Adv. 2016, 6, 11754.
6
7
8
9
(12) Gao, X.; Pan, X.; Gao, J.; Huang, H.; Yuan, G.; Li, Y. Ammonium iodide-induced sulfonylation
of alkenes with DMSO and water toward the synthesis of vinyl methyl sulfones. Chem. Commun. 2015,
51, 210.
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
(13) (a) Zhou, K.; Chen, M.; Yao, L.; Wu, J. Synthesis of sulfonated naphthols via C-H bond
functionalization with the insertion of sulfur dioxide. Org. Chem. Front. 2018, 5, 371. (b) Zhang, J.;
Zhou, K.; Wu, J. Generation of sulfonated isobenzofuran-1(3H)-ones under photocatalysis through the
insertion of sulfur dioxide. Org. Chem. Front. 2018, 5, 813. (c) Zhang, F.; Zheng, D.; Lai, L.; Cheng,
J.; Sun, J.; Wu, J. Synthesis of aromatic sulfonamides through a copper-catalyzed coupling of
aryldiazonium tetrafluoroborates, DABCO·(SO2)2, and N-chloroamines. Org. Lett. 2018, 20, 1167. (d)
Xia, H.; An, Y.; Zeng, X.; Wu, J. A copper-catalyzed sulfonylative C-H bond functionalization from
sulfur dioxide and aryldiazonium tetrafluoroborates. Org. Chem. Front. 2018, 5, 366. (e) Liu, T.; Zheng,
D.; Li, Z.; Wu, J. Synthesis of sulfonated benzo[d][1,3]oxazines by merging photoredox catalysis and
insertion of sulfur dioxide. Adv. Synth. Catal. 2018, 360, 865. (f) Zhou, K.; Xia, H.; Wu, J. Generation
of benzosultams via a radical process with the insertion of sulfur dioxide. Org. Chem. Front. 2017, 4,
1121. (g) Yu, J.; Mao, R.; Wang, Q.; Wu, J. Org. Chem. Front. 2017, 4, 617.
(14) Yang, Y.; Chen, Z.; Rao, Y. The synthesis of diarylsulfones with simple arenes and K2S2O8
through double C-S bond formation. Chem. Commun. 2014, 50, 15037.
(15) Umierski, N.; Manolikakes, G. Arylation of lithium sulfinates with diaryliodonium salts: A
direct and versatile access to arylsulfones. Org. Lett. 2013, 15, 4972.
(16) (a) Cerfontain, H. Sulfur-trioxide sulfonation of aromatic-hydrocarbons. Recl. Trav. Chim.
Pays-Bas. 1985, 104, 153. (b) Mukhopadhyay, S.; Bell, A. T. A high-yield approach to the sulfonation
ACS Paragon Plus Environment

Page 21 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
7
of methane to methanesulfonic acid initiated by H2O2 and a metal chloride. Angew. Chem. Int. Ed.
2003, 42, 2990.
8
9
(17) Sumunnee, L.; Buathongjan, C.; Pimpasri, C.; Yotphan, S. Iodine/TBHP-promoted one-pot
deoxygenation and direct 2-sulfonylation of quinoline n-oxides with sodium sulfinates: facile and
regioselective synthesis of 2-sulfonylquinolines. Eur. J. Org. Chem. 2017, 1025.
(18) Ahammed, S.; Kundu, D.; Siddiqui, M. N.; Ranu, B. C. Metal and solvent free selective
oxidation of sulfides to sulfone using bifunctional ionic liquid [pmim]IO4. Tetrahedron Lett. 2015, 56,
335.
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
(19) Zhang, Z.; Zheng, D.; Ma, N. n.; Bi, J. Brønsted acid-promoted the synthesis of furo[2,3-
b]quinolines. Chin. J. Org. Chem. 2017, 37, 1824.
(20) (a) Duan, W.; Li, J.; Inks, E. S.; Chou, C. J.; Jia, Y.; Chu, X.; Li, X.; Xu, W.; Zhang, Y. Design,
synthesis, and antitumor evaluation of novel histone deacetylase inhibitors equipped with a
phenylsulfonylfuroxan module as a nitric oxide donor. J. Med. Chem. 2015, 58, 4325. (b) Bhunia, S.;
Banerjee, B.; Bhaumik, A. A new hypercrosslinked supermicroporous polymer, with scope for
sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature.
Chem. Commun. 2015, 51, 5020. (c) Budy, S. M.; Loy, D. A. Highly sulfonated polyelectrolytes
through friedel-crafts sulfonylation of polyarylenes. J. Polym. Sci.: Part A: Pol. Chem. 2014, 52, 1381.
(d) McMahon, J. B.; Gulakowski, R. J.; Weislow, O. S.; Schultz, R. J.; Narayanan, V. L.; Clanton, D.
J.; Pedemonte, R.; Wassmundt, F. W.; Buckheit, R. W. Jr.; Decker, W. D. Diarylsulfones, a new
chemical class of nonnucleoside antiviral inhibitors of human immunodeficiency virus type 1 reverse
transcriptase. Antimicrob. Agents Chemother. 1993, 37, 754.
(21) (a) Foschi, F.; Albanese, D.; Pecnikaj, I.; Tagliabue, A.; Penso, M. Regioselective o-
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 25
1
2
3
4
5
6
7
8
9
sulfonylation of N,N-bis(2-hydroxyalkyl)tosylamides as a synthetic key step to enantiopure
morpholines. Org. Lett. 2017, 19, 70. (b) Zhang, X.; Wang, X.; Gao, Y.; Xu, X. Silver-catalyzed formal
[3+2]-cycloaddition of alpha-trifluoromethylated methyl isocyanides: a facile stereoselective synthesis
of CF3-substituted heterocycles. Chem. Commun. 2017, 53, 2427.
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
(22) (a) Gao, W.-C.; Zhao, J.-J.; Hu, F.; Chang, H.-H.; Li, X.; Wei, W.-L. I-2-mediated sulfonylation
and Na2SO3-mediated deacylation: a general protocol for the synthesis of beta-keto sulfones and beta-
dicarbonyl sulfones. Rsc Adv. 2015, 5, 25222. (b) Zhang, X.; Xu, X.; Zhang, D. [3+2] Cycloaddition
of Tosylmethyl Isocyanide with Styrylisoxazoles: Facile Access to Polysubstituted 3-(Isoxazol-5-
yl)pyrroles. Molecules 2017, 22, 1131.
(23) Oroujzadeh, M.; Mehdipour-Ataei, S.; Esfandeh, M. Microphase separated sepiolite-based
nanocomposite blends of fully sulfonated poly(ether ketone)/non-sulfonated poly(ether sulfone) as
proton exchange membranes from dual electrospun mats. Rsc Adv. 2015, 5, 72075.
(24) Farhadi, S.; Zaidi, M. Bismuth ferrite (BiFeO3) nanopowder prepared by sucrose-assisted
combustion method: A novel and reusable heterogeneous catalyst for acetylation of amines, alcohols
and phenols under solvent-free conditions. J. Mol. Catal. A-Chem.2009, 299, 18.
(25) "Dapsone". The American Society of Health-System Pharmacists. Archived from the original
on 2015-01-12. Retrieved Jan 12, 2015. Drugs.com [Internet]. Dapsone Information from Drugs.com;
Available from: https://www.drugs.com/monograph/dapsone.html
(26) (a) Zhu, Y. I.; Stiller, M. J. Dapsone and sulfones in dermatology: Overview and update. J. Am.
Acad. Dermatol. 2001, 45, 420. (b) Sun, Z.-Y.; Botros, E.; Su, A.-D.; Kim, Y.; Wang, E.; Baturay, N.
Z.; Kwon, C.-H. Sulfoxide-containing aromatic nitrogen mustards as hypoxia-directed bioreductive
cytotoxins. J. Med. Chem. 2000, 43, 4160. (c) Deeming, A. S.; Russell, C. J.; Hennessy, A. J.; Willis,
ACS Paragon Plus Environment

Page 23 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
M. C. DABSO-Based, three-component, one-pot sulfone synthesis. Org. Lett. 2014, 16, 150. (d)
Raiziss, G. W.; Clemence, L. W.; Severac, M.; Moetsch, J. C. Chemistry and chemotherapy of 4,4’-
diaminodiphenylsulfone, 4-amino-4’-hydroxy-diphenylsulfone and related compounds. J. Am. Chem.
Soc. 1939, 61, 2763. (e) Lopez de Compadre, R. L.; Pearlstein, R. A.; Hopfinger, A. J.; Seydel, J. K. A
quantitative structure-activity relationship analysis of some 4-aminodiphenyl sulfone antibacterial
agents using linear free energy and molecular modeling methods. J. Med. Chem. 1987, 30, 900.
(27) (a) Alizadeh, A.; Khodaei, M. M.; Nazari, E. Rapid and mild sulfonylation of aromatic
compounds with sulfonic acids via mixed anhydrides using Tf2O. Tetrahedron Lett. 2007, 48, 6805.
(b) Wu, X.-M.; Wang, Y. A mild and base-free synthesis of unsymmetrical diaryl sulfones from
arylboronic acids and arylsulfonyl hydrazides. Synlett 2014, 25, 1163.
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
(28) (a) Wang, L.-J.; Chen, M.; Qi, L.; Xu, Z.; Li, W. Copper-mediated oxysulfonylation of alkenyl
oximes with sodium sulfinates: a facile synthesis of isoxazolines featuring a sulfone substituent. Chem.
Commun. 2017, 53, 2056. (b) Wang, H. Y.; Zhang, X.; Guo, Y. L.; Dong, X. C.; Tang, Q. H.; Lu, L.
Sulfonamide bond cleavage in benzenesulfonamides and rearrangement of the resulting p-
aminophenylsulfonyl cations: application to a 2-pyrimidinyloxybenzylaminobenzenesulfonamide
herbicide. Rapid Commun. Mass Sp. 2005, 19, 1696.
(29) To gain additional evidence for the proposed mechanism, ESI(+)(-)-MS experiments were
performed: see the Supporting Information.
(30) (a) Serwinski, P. R.; Esat, B.; Lahti, P. M.; Liao, Y.; Walton, R.; Lan, J. Photolysis and Oxidation
of Azidophenyl-Substituted Radicals:ꢀ Delocalization in Heteroatom-Based Radicals. J. Org. Chem.
2004, 69, 5247. (b) Chen, S. Y.; Feng, B. Y.; Zheng, X. S.; Yin, J. L.; Yang, S. P.; You, J. S. Iridium-
Catalyzed Direct Regioselective C4-Amidation of Indoles under Mild Conditions. Org. Lett. 2017, 19,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 25
1
2
3
4
5
6
7
8
9
2502. (c) Zeng, H. Y.; Shao, H. W. Convenient synthesis of sulfonyl azides using PEG-400 as an
efficient and eco-friendly reaction medium. Green Chem. Lett. Rev. 2013, 6, 222. (d) Wei, M. E.; Wang,
L. H.; Li, Y. D.; Cui, X. L. Iridium-catalyzed direct ortho-CH amidation of benzoic acids with
sulfonylazides. Chin. Chem. Lett. 2015, 26, 1336.
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
(31) Umierski, N.; Manolikakes, G., Metal-Free Synthesis of Diaryl Sulfones fromArylsulfinic Acid
Salts and Diaryliodonium Salts. Org. Lett. 2013, 15, 188-191.
(32) Umierski, N.; Manolikakes, G. Metal-Free Synthesis of Diaryl Sulfones from Arylsulfinic Acid
Salts and Diaryliodonium Salts. Org. Lett. 2013, 15, 188.
(33) Kumar, D.; Arun, V.; Pilania, M.; Chandra, K. P. A Metal-Free and Microwave-Assisted
Efficient Synthesis of Diaryl Sulfones. Synlett 2013, 24, 831.
(34) Liu, X.; Li W.; Zheng, D.-Q.; Fan X.-N.; Wu, J. Synthesis of sulfones via a reaction of
aryldiazonium tetrafluoroborates, sulfur dioxide, and aryliodoniums. Tetrahedron 2015, 71, 3359.
(35) Khodaei, M. M.; Nazari, E. Sulfonylation of aromatic compounds with methyl p-
toluenesulfonate as a sulfonylating precursor. J. Iran. Chem. Soc. 2012, 9, 507.
(36) Gund, S. H.; Shelkar, R. S.; Nagarkar, J. M. Copper catalyzed synthesis of unsymmetrical diaryl
sulfones from an arenediazonium salt and sodium p-toluenesulfinate. RSC Adv. 2015, 5, 62926.
(37) Lucchi, O. D.; Marcgioro G. Synthesis and diels-alder reactions of 2,3-bis(benzenethio)-1,3-
butadiene. Phosphorus Sulfur 1985, 24, 305.
(38) Karimi, B.; Khorasani, M.; Rostami, F. B.; Elhamifar, D.; Vali, H. Tungstate Supported on
Periodic Mesoporous Organosilica with Imidazolium Framework as an Efficient and Recyclable
Catalyst for the Selective Oxidation of Sulfides. ChemPlusChem 2015, 80, 990.
(39) Bandgar, B. P.; Bettigeri, S. V.; Phopase, J. Unsymmetrical Diaryl Sulfones through Palladium-
ACS Paragon Plus Environment

Page 25 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Catalyzed Coupling of Aryl Boronic Acids and Arylsulfonyl Chlorides. Org. Lett. 2004, 6, 2105.
(40) Lutz, M.; Wenzler, M.; Likhotvorik, I. An Efficient Oxidation of Sulfides to Sulfones with
Urea–Hydrogen Peroxide in the Presence of Phthalic Anhydride in Ethyl Acetate. Synthesis 2018, 50,
2231.
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
(41) Peng, Y. Synthesis of symmetrical diaryl sulfone by homocoupling of sodium arylsulfinate. J.
Chem. Res. 2014, 38, 265.
(42) Bahrami, K.; Khodei, M. M.; Shahbazi, F., Highly selective catalytic Friedel–Crafts
sulfonylation of aromatic compounds using a FeCl3-based ionic liquid. Tetrahedron Lett. 2008, 49,
3931.
ACS Paragon Plus Environment