Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives

Article abstract of DOI:10.1021/acs.orglett.0c02370

A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones, respectively. The nucleophilic addition of two molecular sulfoxonium ylides to construct sulfone-substituted 1,4-dione compounds is the highlight of this work.

Full text of DOI:10.1021/acs.orglett.0c02370

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Letter
Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and
Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl
Sulfursulfoxonium Ylides, and β‑Keto Thiosulfones Derivatives
Fei Wang, Bo-Xi Liu, Weidong Rao, and Shun-Yi Wang*
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ABSTRACT: A diverse chemoselective insertion reaction of
sulfoxonium ylides and thiosulfonates under transition-metal-free
conditions is developed, which successfully affords 1,4-diketone
compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones,
respectively. The nucleophilic addition of two molecular sulfoxo-
nium ylides to construct sulfone-substituted 1,4-dione compounds is
the highlight of this work.
ulfur compounds are widely found in natural products,
S
pharmaceutical molecules, and functional materials.1
Sulfone compounds have been utilized as indispensable
building blocks in modern organic chemistry. Due to their
special electronic characteristics and unique structural proper-
ties, they have been widely applied in the conversion and
synthesis of various drugs.2 In recent years, thiosulfonates have
been widely used in the construction of sulfur-containing
compounds due to their high reactivity. Common reactions
include nickel-catalyzed reductive coupling reactions to build
C−S bonds,3 transition-metal-catalyzed C−S bond construc-
tion reactions,4 and S-radical processes to build C−S bonds or
sulfone compounds.5 Synthesis of sulfone compounds from
bench stable thiosulfonates is intriguing.
Figure 1. Metal-free catalysis of sulfoxonium ylides and present work.
successfully affords 1,4-diketone compounds, arylthiosulfoxide-
ylides and β-keto thiosulfones, respectively (Figure 1, eq 2).
We consulted relevant literature and found that Xu, Jiang et al.
have reported the use of thiosulfonates to react with different
substrates to prepare β-keto thiosulfones.13 However, sulfone
substituted 1,4-diketone compounds and aryl sulfursulfoxo-
nium ylides have not been reported to date.
Initially, we tried the reaction of β-ketosulfoxonium ylide 1a,
S-phenyl benzenesulfonothioate 2a, and Phenanthroline (10
mol %) in MeCN at room temperature for 24 h. Gratifyingly,
the reaction proceeded smoothly to give the 1,4-diphenyl-2-
(phenylsulfonyl)but-2-ene-1,4-dione 3a. First, we investigated
the effect of temperature on the reaction. It was found that 3a
was obtained in 62% yield when the temperature was increased
In the past few years, as a kind of important carbene
precursor, sulfoxonium ylides attracted great attention due to
their diverse applications in organic synthesis. Compared to
traditional diazo compounds, sulfoxonium ylide is easier to
prepare and bench stable. It is considered an important
alternative to diazo compounds for its high reactivity. In recent
years, the use of sulfoxonium ylides as the C1 or C2 synthons
under the catalysis of transition metals (such as rhodium,
ruthenium, cobalt, palladium, iridium, and other metals) has
successfully achieved the activation of sp2 C−H bonds of aryl
groups6 and the synthesis of various heterocyclic compounds
such as furan,7 indole,8 quinoline,9 pyrrole,10 and pyrimidine.11
In 2019, Xu’s group reported the reaction of sulfoxonium
ylides with diazo compounds to prepare highly functionalized
hydrazone compounds (Figure 1, eq 1).12 We made a
preliminary attempt to react thiosulfonates with sulfoxonium
ylides. Surprisingly, unexpected sulfone-substituted 1,4-dicar-
bonyl compounds were observed instead of the proposed β-
ketosulfide compounds. Herein, we describe a diverse
chemoselective insertion reaction of sulfoxonium ylides and
thiosulfonates under transition-metal-free conditions, which
Received: July 16, 2020
https://dx.doi.org/10.1021/acs.orglett.0c02370
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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a b
,
to 80 °C (Table 1, entries 1−3). We also investigated the effect
of 1,10-phenanthroline as the additive. Removing 1,10-
Scheme 1. Substrate Scope
a b
,
Table 1. Optimization of the Reaction Conditions
b
entry
T (°C)
solvent
MeCN
MeCN
MeCN
MeCN
DMF
yield (%)
1
2
3
60
80
100
80
80
80
80
80
80
80
42
62
44
52
56
63
65
65
70
62
messy
90(6a)
c
4
5
6
7
8
DMA
DMSO
DMSO/DMF
DMSO
DMSO
Dioxane
Dioxane
d
9
e
10
f
11
100
100
g
12
a
Reaction conditions: 1a (0.5 mmol), 2a (0.2 mmol), 1,10-phen (10
b
c
mol %), solvent (1 mL), 24 h. Isolated yield. Without 1,10-phen.
d
e
f
g
DMSO (0.5 mL). DMSO (2 mL). Et3N (2.0 equiv). Cs2CO3 (2.0
equiv).
a
phenanthroline led to 3a in a slightly lower yield, which
indicates that 1,10-phenanthroline has a positive effect on the
increasing yield (Table 1, entry 4). We also examined the
effects of other additives, which are not as effective as 1,10-
phenanthroline (for details, see Supporting Information). Next,
we screened several solvents such as DMF, DMA, and DMSO.
3a was obtained in 65% yield when the reaction was carried
out in DMSO (Table 1, entries 5−8). We examined the effect
of the amount of solvent on the reaction afterward. Reducing
the solvent from 1 to 0.5 mL resulted in 3a in 70% yield (Table
1, entries 9−10). Therefore, the optimized reaction conditions
are as follows: β-ketosulfoxonium ylide 1a (0.5 mmol), S-
phenyl benzenesulfonothioate 2a (0.2 mmol), and phenanthro-
line (10 mol %) in 0.5 mL DMSO at 80 °C for 24 h. To our
delight, when we added Cs2CO3 (2.0 equiv), another product
was detected, after NMR, IR, and HRMS analysis. It was found
that 1-phenyl-2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one
6a was observed. However, the reaction system was messy
when an organic base instead of Cs2CO3 was added (Table 1,
entry 11). After a series of conditions optimization, the
optimized reaction conditions were obtained: β-ketosulfoxo-
nium ylide 1a (0.4 mmol), S-phenyl benzenesulfonothioate 2a
(0.2 mmol), and phenanthroline (10 mol %) in dioxane at 100
°C for 24 h. The target product 6a was obtained in 90% yield
under the optimized conditions (Table 1, entry 12).
Reaction conditions: substituted sulfoxonium slides 1 (0.5 mmol),
substituted thiosulfonates 2 (0.2 mmol), 1,10-phenanthroline (0.02
b
mmol), DMSO (0.5 mL), 80 °C, 24 h. Isolated yields.
proceed to afford 3g, 3h, and 3i in 40%, 40%, and 50% yields,
respectively. When S-phenyl naphthalene-2-sulfonothioate 2j
was applied to the reaction, the target product 3j was obtained
in 65% yield. The reaction of S-phenyl 4-acetamidobenzene-
sulfonothioate 2k with 1a furnished 3k in 60% yield. Then, we
investigated the reactions of alkyl thiosulfonates. It should be
noted that S-phenylmethanesulfonate 2l could also proceed
smoothly to give 3l in 50% yield. These results show that the
thiosulfonate substrates have good generality and high
functional group tolerance.
Next, we examined the substrate scope of sulfoxonium ylides
(Scheme 1). Unfortunately, 2-(dimethyl(oxo)-λ6-sulfanyli-
dene)-1-(o-tolyl)ethan-1-one failed to afford the desired 4a
for the steric effect. The reaction of 2-(dimethyl(oxo)-λ6-
sulfanylidene)-1-(m-tolyl)ethan-1-one 1b reacted with 2a
successfully to afford 4b in 60% yield. However, there is a
decrease in the yield when the 2-(dimethyl(oxo)-λ6-sulfanyli-
dene)-1-(p-tolyl)ethan-1-one 1c was used. The target product
4c was obtained in 20% yield. We further investigated the
effects of halogen substitution on the benzene ring. When 3-Cl,
4-Cl, 4-F substituted sulfoxonium ylides were applied to the
reactions, the desired products 4d, 4e, and 4f were obtained in
50%, 52%, and 55% yields, respectively. Unfortunately, the
reaction of sulfoxonium ylide bearing a strong electron-
withdrawing group (4-NO2) could not afford the target
product 4g. When the naphthalene ring and thiophene-
substituted sulfoxonium ylides 1i and 1j were used, the desired
products 4h and 4i could be obtained in 60% and 55% yields,
respectively. When cinnamyl sulfoxonium ylide was subjected
to the reaction, 4j was not obtained.
With the optimal conditions in hand, we explored the scope
of thiosulfonates (Scheme 1). First, we examined the reactivity
of different substituted thiosulfonates. The reaction of S-phenyl
4-methylbenzenesulfonate 2b with 1a gave the target product
3b in 65% yield. When S-phenyl arylsulfonates bearing halogen
groups (F, Cl, Br) were subjected to the reaction, the desired
products 3c, 3d, and 3e were obtained in 60−70% yields. The
reaction of S-phenyl 4-(trifluoromethyl)benzenesulfonothioate
2f led to 3f in 56% yield. It was found that the reactions of S-
phenyl 4-tert-butylbenzenesulfonate 2g and heterocycle-
functionalized thiosulfonates 2h and 2i with 1a could also
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a
Next, we tried to investigate the reactivity of alkyl-
substituted sulfoxonium ylides. When 1-cyclohexyl-2-
(dimethyl(oxo)-λ6-sulfanylidene)ethan-1-one was used, it was
found that the reaction was very messy. To our delight, the
product 5a could be obtained in 96% yield when we decrease
the reaction temperature to 40 °C. With the optimal
conditions in hand, we explored the scope of thiosulfonates
(Scheme 2). It should be noted that whether it is a methyl-
Scheme 3. Substrate Scope
a b
,
Scheme 2. Substrate Scope
a
Reaction conditions: substituted sulfoxonium slides 1 (0.4 mmol),
substituted thiosulfonates 2 (0.2 mmol), 1,10-phenanthroline (0.02
mmol), Cs2CO3 (2.0 equiv), 1,4-dioxane (1.0 mL), 100 °C, 24 h.
Scheme 4. Related Derivative Reactions
a
Reaction conditions: substituted sulfoxonium slides 1 (0.3 mmol),
substituted thiosulfonates 2 (0.2 mmol), 1,10-phenanthroline (0.02
mmol), DMSO (1.0 mL), 40 °C, 4 h. Isolated yields.
b
scaled up the template reaction to 3 mmol scale, the yield
slightly decreased, and the target product 3a was obtained in
55% yield. Based on the literature,14 we attempted the reaction
of 3a and TMSBr. The brominated product 7a could be
obtained in 51% yield.
substituted thiosulfonate or an electron-withdrawing group
functionalized thiosulfonate, or a halogen or heterocyclic-
substituted thiosulfonates were used, the desired products 5b−
e could be obtained in excellent yields, respectively. We also
investigated the reactivity of Se-phenyl benzenesulfonosele-
noate. To our delight, the target product 5f was obtained in
44% yield. Unfortunately, the reaction of alkyl thiosulfonates
was not efficient. Then, we investigated the reactivity of
different substituted alkyl sulfoxonium ylides. The reaction of
1-(dimethyl(oxo)-λ6-sulfanylidene)-3-phenylpropan-2-one
underwent somoothly to give the target product 5i in 84%
yield. Due to the effect of steric hindrance, 1-(dimethyl(oxo)-
λ6-sulfanylidene)-3-methylbutan-2-one is more reactive than 1-
(dimethyl(oxo)-λ6-sulfanylidene)-3,3-dimethylbutan-2-one. 5j
and 5k were observed in 84% and 57% yields, respectively.
However, when benzyl (S)-(4-(dimethyl(oxo)-λ6-sulfanyli-
dene)-3-oxobutan-2-yl)carbamate was used, the target product
5l could not be obtained.
Finally, we examined the substrate universality of product 6
(Scheme 3). S-(p-Tolyl) benzenesulfonothioate and S-(tert-
butyl) 4-methylbenzenesulfonothioate reacted well with 2a in
the presence of Cs2CO3 in 1,4-dioxane which led to the desired
products 6b and 6c in 45% and 40% yields, respectively. Then
we examined the substrate universality of different substituted
sulfoxonium ylides. When 2-(dimethyl(oxo)-λ6-sulfanylidene)-
1-(m-tolyl)ethan-1-one, 2-(dimethyl(oxo)-λ6-sulfanylidene)-1-
(4-fluorophenyl)ethan-1-one, and 1-cyclohexyl-2-(dimethyl-
(oxo)-λ6-sulfanylidene)ethan-1-one were utilized, the target
products 6d, 6e, and 6f were obtained in 60%, 50%, and 40%
yields, respectively.
In order to further understand the reaction mechanism, we
conducted a series of control experiments (for details, see
Supporting Information). Through a series of experiments we
speculated that the reaction may have undergone a free radical
reaction. To gain deep insight into the radical formation and
the role of 1,10-phenanthroline, electron paramagnetic spec-
troscopy (EPR) experiments were performed in the presence
of 5,5-dimethyl-1-pyrrolidine-noxide (for details, see Support-
ing Information). Through experiments, we successfully
confirmed that the reaction is a free radical reaction process
and 1,10-phenanthroline plays a role in stabilizing free radicals.
Based on the above experimental results and previous
reports,12,15 we propose a plausible mechanism in Scheme 5.
First, homolysis of 2a gives sulfone radical I and a phenylthio
radical. In route 1, self-coupling of the phenylthio radical
affords diphenyl disulfide. I reacts with sulfur ylide 1a to
generate sulfur radical intermediate II. Intermediate II is
oxidized to afford ionic intermediate III in DMSO under air
conditions. Next, intermediate III protonated to afford cationic
intermediate IV.15a Cationic intermediate IV reacts with
another 1a to form cationic intermediate VIII and releasing
a molecule of dimethyl sulfoxide.15c
Subsequently, intermediate VIII isomerizes to intermediate
IX.15c Finally, intermediate IX releases a molecule of dimethyl
sulfoxide to furnish target product 3a. On the other hand, in
route 2, intermediate III isomerizes to intermediate V. Then
intermediate V forms a carbene intermediate VI in the
presence of base.15d Then intermediate VI reacts with the
phenylthio radical to form radical intermediate VII. Inter-
mediate VII protonated to afford target product 6a. In route 3,
In order to explore further application of this reaction, we
tried the scale-up reaction of 1a with 2a (Scheme 4). When we
C
https://dx.doi.org/10.1021/acs.orglett.0c02370
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Letter
Materials Science & Collaborative Innovation Center of Suzhou
Nano Science and Technology, Soochow University, Suzhou
215123, China
Scheme 5. A Plausible Mechanism
Weidong Rao − Jiangsu Provincial Key Lab for the Chemistry
and Utilization of Agro-Forest Biomass, College and Chemical
Engineering, Nanjing Forestry University, Nanjing 210037,
China; orcid.org/0000-0002-6088-7278
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c02370
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Natural Science
Foundation of China (Nos. 21971174, 21772137), PAPD,
the Project of Scientific and Technologic Infrastructure of
Suzhou (No. SZS201708), the Major Basic Research Project of
the Natural Science Foundation of the Jiangsu Higher
Education Institutions (No. 16KJA150002), Postgraduate
Research & Practice Innovation Program of Jiangsu Province
(No. KYCX17_1980), Soochow University, and State and
Local Joint Engineering Laboratory for Novel Functional
Polymeric Materials for financial support.
the phenylthio radical reacts with cyclohexylthioylide to form
sulfur radical intermediate X. Intermediate X is oxidized to
ionic intermediate XI in DMSO under air conditions. Finally,
intermediate XI isomerizes to target product 5a (Scheme 5).
In summary, we have developed tandem radical reactions of
sulfoxonium ylide and thiosulfonate under transition-metal-free
conditions. By adjusting the reaction conditions, we can
selectively prepare highly functionalized 1,4-diketones, arylth-
iosulfoxide-ylides, and β-keto thiosulfones. The reaction has
advantages of a broad substrate scope, mild reaction
conditions, and simple operation. The excellent substrate
universality provides a novel and simple new method for the
preparation of sulfone-substituted 1,4-dicarbonyl compounds.
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Detailed experimental procedures and characterization
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AUTHOR INFORMATION
Corresponding Author
■
Shun-Yi Wang − Key Laboratory of Organic Synthesis of Jiangsu
Province, College of Chemistry, Chemical Engineering and
Materials Science & Collaborative Innovation Center of Suzhou
Nano Science and Technology, Soochow University, Suzhou
215123, China; orcid.org/0000-0002-8985-8753;
Email: shunyi@suda.edu.cn
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Fei Wang − Key Laboratory of Organic Synthesis of Jiangsu
Province, College of Chemistry, Chemical Engineering and
Materials Science & Collaborative Innovation Center of Suzhou
Nano Science and Technology, Soochow University, Suzhou
215123, China
Bo-Xi Liu − Key Laboratory of Organic Synthesis of Jiangsu
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