An Unexpected Domino Reaction of β-Keto Sulfones with Acetylene Ketones Promoted by Base: Facile Synthesis of 3(2H)-Furanones and Sulfonylbenzenes

Article abstract of DOI:10.1002/adsc.201700830

An unexpected domino reaction of β-keto sulfones with acetylene ketones has been developed. The domino reaction of β-keto sulfones with diynones proceeded smoothly in the presence of 30 mol% K₂CO₃ without other additives, and afforded the novel 3(2H)-furanone derivatives. On replacing the diynones with terminal alkyne ketones, the reaction regioselectivity was changed and sulfonylbenzenes were obtained via benzannulation in good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.201700830

Title: An Unexpected Domino Reaction of β-Keto Sulfones with
Acetylene Ketones Promoted by Base: Facile Synthesis of 3(2H)-
Furanones and Sulfonylbenzenes
Authors: Wei Tong, Qian-yu Li, Yanli Xu, Heng-shan Wang, Yan-yan
Chen, and Ying-ming Pan
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700830
Link to VoR: http://dx.doi.org/10.1002/adsc.201700830

10.1002/adsc.201700830
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
An Unexpected Domino Reaction of β-Keto Sulfones with
Acetylene Ketones Promoted by Base: Facile Synthesis of 3(2H)-
Furanones and Sulfonylbenzenes
Wei Tong,a Qian-Yu Li,a Yan-Li Xu,b Heng-Shan Wang,a Yan-Yan Chen,b, * and Ying-
Ming Pana, *
a
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and
Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, People’s Republic of China.
E-mail: panym@mailbox.gxnu.edu.cn
College of Pharmacy, Guilin Medical University, Guilin, 541004, People’s Republic of China.
b
E-mail: chenyy1988@glmc.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. An unexpected domino reaction of β-keto sulfones obtained via the benzannulation in good yields.
with acetylene ketones has been developed. The domino
reaction of β-keto sulfones with diynones proceeded
smoothly in the 30% mol K2CO3 without other additives, and
afforded the novel 3(2H)-furanone derivatives. Replaced
diynones with terminal alkyne ketones, the reaction
regioselectivity was changed and sulfonylbenzenes were
Keywords: domino reaction; β-keto sulfones; acetylene
ketones; reaction regioselectivity; 3(2H)-furanones;
sulfonylbenzenes
ketones (Scheme 1). In this work, the base-induced
domino reactions of β-keto sulfones with diynones
afforded a series of sulfonylvinyl-containing 3(2H)-
furanone derivatives which are an unexplored class of
compounds and predicted to possess biological
activities duo to the combination of active groups
Introduction
Sulfones are considered as an important class of
organic compounds in both synthetic and medicinal
chemistry because of their various applications in
synthesis[1] and versatile biological activities[2].
Among sulfone derivatives, great attention is drawn
to β-keto sulfones[3] as their different functional
groups (ketone and sulfone). β-Keto sulfones are
important intermediates that have been used for the
preparation of different classes of organic compounds
such as alkenes (Julia Kocienski olefination)[4],
alkynes[5], chalcones[6], 2,3-dihydrofurans[7], 1,2,3-
triazoles[8], pyrroles[9] and 4H-pyrans[10]. In the past
years, great effort has been focus on the Michael
reaction of β-keto sulfones with conjugated olefins.[11]
In contrast, the additions of β-keto sulfones with
alkynes have been scarcely explored. Yamamoto[12]
reported the allylation of carbon nucleophiles with
alkynes under the catalysis of palladium/acetic acid.
Takai[13] found that δ-keto sulfones were obtained via
the additions of β-keto sulfones with terminal alkynes
promoted by rhenium catalyst.
sulfonylvinyl[17] and
3(2H)-furanone
core[18]
.
Furthermore, we achieved the transformation of
reaction regioselectivity by replacing diynones with
terminal alkyne ketones, and highly substituted
sulfonylbenzene derivatives were obtained via the
benzannulation reaction.
Recently, we have studied the coupling of
acetylene ketones with trimethylsilyl azide[14], glycine
esters[15] and water[16]. In this context, we focus on the
Michael additions of β-keto sulfones and acetylene
Scheme 1. The base-promoted domino reactions of β-keto
sulfones with acetylene ketones.
1
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
Results and Discussion
Table 2. Substrate scope for the domino reaction of β-keto
sulfones and diynones. [ a, b]
Initially, the Michael addition of 1-(methylsulfonyl)-
propan-2-one 1a with 1,5-diphenylpenta-1,4-diyn-3-
one 2a was investigated. When the reaction was
treated with 30% mol Cs2CO3 in 1,4-Dioxane at 75
oC, an unexpected product 3a was obtained in 65%
yield (Table 1, entry 1). Then the reaction conditions
were further optimized and results are summarized in
Table 1. K2CO3 was found to be the most suitable
base and the yield is up to 75% (Table 1, entries 2-5).
The decrease of K2CO3 amount resulted in the serious
loss of yield (Table 1, entry 6), and the increase of
K2CO3 loading hadn’t significant impact on the yield
of 3a, so we chose 30% mol K2CO3 according to the
economic principle (Table 1, entries 7 and 8).
Solvents were also investigated, 1,4-Dioxane proven
to be the most suitable solvent, other solvents such as
Toluene, DMSO, THF, DMF, EtOH and CH3CN are
incompatible with the reaction (Table 1, entries 9-14).
Table 1. Optimization of the domino reaction conditions. [a]
[a]
Reaction conditions: 1 (0.36 mmol), 2 (0.3 mmol),
K2CO3 (0.09 mmol), 1,4-Dioxane (2 mL), 75 oC, 0.5 h.
[b] Isolated yield.
Entry
1
Base
Solvent
Yield (%)[b]
65
Cs2CO3
KOH
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
Toluene
2
40
The increase or decrease of temperature is
unfavorable for the reaction (Table 1, entries 15 and
16).
3
Et3N
trace
34
4
t-BuOK
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
With the optimal reaction conditions in hand, the
substrate scope was examined by using various β-
keto sulfones and diynones, and results are
summarized in Table 2. The aromatic diynones
bearing an alkyl on the benzene ring reacted
smoothly, and afforded the desired products in high
yields (Table 2, 3b-3f). The structure of 3c was
confirmed by X-ray crystal structure analysis (Fig. 1).
The 3-MeOC6H4 substituent resulted in the light drop
in the yield, 3g was obtained in 55% yield. The 4-
FC6H4 substituent gave 3h in moderate yield 60%.
The thienyl led to significant drop in the yield and 3i
was prepared in 30% yield. The alkyl diynones are
tolerant and good yields were observed (Table 2, 3j-
3l). In the β-keto sulfone moiety, the substrates with a
phenyl substituent in R2 position generated the
corresponding products in high yields (Table 2, 3m-
3o). The R1 as other substituents was also tested, the
tert-butyl provided 3p in excellent yield, the 4-
ClC6H4 resulted in the serious loss of yield and gave
3q in 42% yield.
5
75
6[c]
7[d]
8[e]
9
30
74
76
n.r.[f]
n.r.
55
10
11
12
13
14
15[g]
DMSO
THF
DMF
trace
n.r.
20
EtOH
CH3CN
1,4-Dioxane
1,4-Dioxane
10
16[h]
20
[a]
Reaction conditions: 1a (0.24 mmol), 2a (0.2 mmol),
base (0.06 mmol), solvent (2 mL), 75 oC, 1 h.
[b] Isolated yield.
[c] With 10% mol K2CO3.
[d] With 50% mol K2CO3.
[e] With 100% mol K2CO3.
[f] n.r. = No reaction.
[g] The reaction was carried out at 90 oC.
[h] The reaction was carried out at 50 oC.
Interestingly, the treatment of 1-(methylsulfonyl)-
propan-2-one 1a with 1-phenylpenta-1,4-diyn-3-one
2
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
Table 3. Substrate scope for the benzannulation. [ a, b]
3c
7ea
Fig 1. X-ray crystal structures of 3c and 7ea.
4aa in the same condition gave an unexpected
product 5aa in 80% yield (Scheme 2). Replaced 4aa
with 4ab, 4ac and 4ad, no product was obtained, and
4ab was easy to decompose under the standard
condition. We speculated that only alkyne ketones
were well compatible with the benzannulation. Then
the 1-phenylprop-2-yn-1-one 4a was employed, and
the reaction proceeded smoothly. Therefore, the
reaction of 1a with 4a was chosen as the model
reaction to further optimize the conditions (see
Supporting Information). Finally, the optimum
conditions of benzannulation are 30% mol K2CO3 in
DMF at 75 oC for 0.5 h.
The substrate scope of the benzannulation was
examined and results are showed on the Table 3.
Terminal alkyne ketones bearing various aromatic
substituents were well tolerated. In detail, the
electron-donating and electron-withdrawing groups
on the benzene ring gave moderate yields (Table 3,
5a-5g). The ortho substitutions on the benzene ring
hadn’t obvious effect on the reactivity and yield
(Table 3, 5h and 5i). The naphthyl substituent
generated 5j in 70% yield. When 1-(thiophen-2-
yl)prop-2-yn-1-one 4k as substrate, no desired
product 5k was observed. Alkyl-substituted terminal
alkyne ketones are suitable, 5l and 5m were obtained
[a]
Reaction conditions: 1 (0.25 mmol), 4 (0.6 mmol),
K2CO3 (0.075 mmol), DMF (2 mL), 75 oC, 0.5 h.
[b] Isolated yield.
in 75% and 73%, respectively. Di-substituted alkyne
ketones were also examined, but no products were
obtained (5n and 5o), we speculated the sterically
hindered substrates were unfavorable in the
benzannulation. In the β-keto sulfone moiety, phenyl
substituents in R1 and R2 positions also led to the
benzannulation successfully, products were obtained
in moderate yields (Table 3, 5p-5v).
The domino reactions of other carbonyl
compounds with acetylene ketones were also studied
(Scheme 3). In the reaction of α-nitroketones with 2a,
no product was detected (Scheme 3, eq. (1)). β-Keto
sulfoxide is incompatible with 2a, the reaction was
complicated and no major product was obtained
(Scheme 3, eq. (2)). The Michael additions of β-
dicarbonyl compounds with diynones afforded
cyclopentenones as products (Scheme 3, eq. (3)). The
structure of 7ea was confirmed by X-ray crystal
structure analysis (Fig 1). In the reactions of α-
nitroketone, β-keto sulfoxide and β-dicarbonyl
compounds with 4a, no product or no major products
were observed (Scheme 3, eq. (4)-(6)). We found that,
compared with other carbonyl compounds, the
sulfone was helped to cleavage the carbon-carbon
single bond and efficiently improved the reaction
regioselectivity.
Scheme 2. The benzannulation of 1a with terminal alkynes.
3
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
obtained in 30% yield and trace 5ak was detected by
LC/MS, no 5k was observed (see Supporting
Information). Compared with alkyl alkyne ketone, the
β-keto sulfone tended to react with phenyl alkyne
ketone. On the other way, the cross reaction of 1a, 4g
and 4x provided 5g in 38% yield and trace 5gx and
5x (see Supporting Information). The trifluoromethyl
is more favorable than the methoxyl in the
benzannulation, because the electron-withdrawing
substituent is more compatible with the Michael
addition.
The proposed pathways for the domino reactions of
β-keto sulfones and acetylene ketones are proposed in
Scheme 5. For the pathway I: the base-induced
Michael addition of 1a and 2a generated the
intermediate A. Then the intermediate A occurred
intramolecular cycloaddition and gave the
intermediate B. Duo to the ring strain, the
cyclobutene intermediate B was easy to open ring and
generated the intermediate D.[13, 19] After the second
addition, the 3(2H)-furanone 3a was obtained. For the
pathway II [20]: the base-induced Michael addition of
1a and 4a afforded the intermediate F. Then the
intermediate F reacted with another molecule 4a and
gave the intermediate G. The intramolecular
cyclization of G generated the intermediate H.
Finally, the product 5a was obtained via the H-
abstraction and dehydration of H.
Scheme 3. The domino reactions of other carbonyl
compounds with acetylene ketones.
To studied the domino reaction of β-keto sulfones
with acetylene ketones, some competitive
experiments were carried out (Scheme 4). Firstly, the
reaction of unsymmetrical diynones with 1a was
examined, no product was detected (Scheme 4, eqs.
(1) and (2)). The stronger bases and the long reaction
time were tried, but resulted in the diynones
decomposition. Unsymmetrical diynones were
unsuitable in this reaction. Secondly, the cross
reaction of 1a, 4a and 4k was investigated, 5a was
Scheme 5. Proposed pathways for domino reactions of β-
keto sulfones with acetylene ketones.
Conclusion
In summary, we have established a domino reaction
of β-keto sulfones with acetylene ketones promoted
by 30% mol K2CO3 without any other additives. The
domino
reactions
generated
3(2H)-furanone
Scheme 4. Competitive experiments
derivatives and sulfonylbenzenes in excellent yields.
Furthermore, the 3(2H)-furanone compounds are
4
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
37.8, 24.3, 24.3, 15.6, 13.8, 13.8. HRMS (m/z) (ESI): calcd
for C27H31O4S 451.1943 [M+H]+, found 451.1932.
currently used for biological activity test to study the
potential biological activities in our laboratory.
2-((Z)-4-(tert-butyl)benzylidene)-4-((Z)-1-(4-(tert-
butyl)phenyl)-2-(methylsulfonyl)vinyl)-5-methylfuran-
3(2H)-one (3e): yellow oil (122.1 mg, 85%). H NMR
Experimental Section
1
(400 MHz, CDCl3) δ 7.77 (d, J = 8.5 Hz, 2H), 7.47 (d, J =
8.5 Hz, 2H), 7.39 (d, J = 10.0 Hz, 4H), 6.86 (s, 1H), 6.82 (s,
1H), 3.15 (s, 3H), 2.16 (s, 3H), 1.33 (d, J = 11.9 Hz, 18H).
13C NMR (100 MHz, CDCl3) δ 184.6, 178.4, 154.5, 154.0,
145.1, 143.6, 134.1, 131.6, 129.4, 128.9, 128.2, 127.2,
126.2, 126.0, 125.9, 115.3, 114.4, 42.8, 35.0, 34.8, 31.1,
31.1, 15.6. HRMS (m/z) (ESI): calcd for C29H35O4S
479.2256 [M+H]+, found 479.2253.
General experimental procedure for the synthesis of
3(2H)-furanones 3.
A solution of 1 (0.36 mmol), 2 (0.3 mmol), K2CO3 (0.09
mmol) and 1,4-Dioxane (2 mL) in a 15 mL test tube was
o
stirred at 75 C for 30 min. Then the mixture was diluted
with water (30 mL) and extracted with ethyl acetate (3 ×
30 mL). The combined organic layers were dried with
anhydrous Na2SO4 and concentrated under reduced
pressure. The residue was purified by flash column
chromatography to give 3.
5 - m e t h y l - 4 - ( ( Z ) - 2 - ( m e t h y l s u l f o n y l ) - 1 - ( 4 -
pentylphenyl)vinyl)-2-((Z)-4-pentylbenzylidene)furan-
1
3(2H)-one (3f): yellow oil (89.6 mg, 82%). H NMR (400
2-((Z)-benzylidene)-5-methyl-4-((Z)-2-(methylsulfonyl)-
1-phenylvinyl)furan-3(2H)-one (3a): yellow solid (82.4
MHz, CDCl3) δ 7.74 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8.2
Hz, 2H), 7.26 (s, 2H), 7.20 (d, J = 8.2 Hz, 2H), 6.85 (s,
1H), 6.80 (s, 1H), 3.16 (s, 3H), 2.67–2.61 (m, 4H), 2.14 (s,
3H), 1.66–1.60 (m, 4H), 1.36–1.30 (m, 8H), 0.91–0.87 (m,
6H). 13C NMR (100 MHz, CDCl3) δ 184.6, 178.3, 150.5,
146.7, 146.3, 146.0, 145.0, 143.7, 134.5, 133.2, 131.7,
129.6, 129.2, 129.1, 129.1, 128.1, 127.4, 115.5, 114.5,
42.8, 40.1, 35.9, 35.6, 31.4, 31.4, 30.8, 30.8, 22.5, 22.4,
15.6, 13.9. HRMS (m/z) (ESI): calcd for C21H17O4S
507.2569[M+H]+, found 507.2564.
o
1
mg, 75%), mp: 182.2–183.5 C. H NMR (400 MHz,
CDCl3) δ 7.83 (dd, J = 7.8, 1.7 Hz, 2H), 7.43 (ddd, J = 7.1,
4.2, 1.6 Hz, 8H), 6.87 (s, 1H), 6.81 (s, 1H), 3.18 (s, 3H),
2.13 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 184.6, 178.7,
145.3, 143.6, 137.4, 131.7, 130.8, 130.4, 129.2, 129.2,
129.0, 127.6, 115.6, 114.4, 42.8, 15.6. HRMS (m/z) (ESI):
calcd for C21H19O4S 367.1004 [M+H]+, found 367.0995.
5-methyl-2-((Z)-4-methylbenzylidene)-4-((Z)-2-
(methylsulfonyl)-1-(p-tolyl)vinyl)-furan-3(2H)-one (3b):
o
1
2 -(( Z)- 3 - me t h o xy be nz y li d e ne ) -4 -(( Z)- 1 -( 3 -
methoxyphenyl)-2-(methylsulfonyl)vinyl)-5-
methylfuran-3(2H)-one (3g): brown oil (70.4 mg, 55%).
1H NMR (400 MHz, CDCl3) δ 7.33–7.18 (m, 5H), 6.94 –
6.84 (m, 5H), 6.73 (s, 2H), 3.76–3.74 (m, 3H), 3.72 (d, J =
4.3 Hz, 3H), 3.09 (s, 3H), 2.05 (d, J = 2.4 Hz, 3H). 13C
NMR (100 MHz, CDCl3) δ 184.5, 178.7, 160.0, 159.7,
145.3, 143.4, 138.7, 132.8, 130.2, 129.9, 129.2, 124.4,
110.0, 116.6, 116.2, 116.2, 115.5, 114.3, 113.0, 55.4, 55.3,
42.7, 15.6. HRMS (m/z) (ESI): calcd for C23H23O6S
427.1215 [M+H]+, found 427.1209.
yellow solid (94.7 mg, 80%), mp: 153.4–155.5 C. H
NMR (400 MHz, CDCl3) δ 7.72 (d, J = 8.1 Hz, 2H), 7.32
(d, J = 8.1 Hz, 2H), 7.25 (d, J = 9.5 Hz, 2H), 7.20 (d, J =
8.0 Hz, 2H), 6.84 (s, 1H), 6.78 (s, 1H), 3.17 (s, 3H), 2.39
(d, J = 9.0 Hz, 6H), 2.13 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 184.6, 178.4, 145.0, 143.7, 141.4, 141.0, 134.4,
131.8, 129.8, 129.8, 129.0, 128.1, 127.5, 115.6, 114.6, 42.8,
21.4, 15.6. HRMS (m/z) (ESI): calcd for C23H23O4S
395.1317 [M+H]+, found 395.1308.
2-((Z)-4-ethylbenzylidene)-4-((Z)-1-(4-ethylphenyl)-2-
(methylsulfonyl)vinyl)-5-methylfuran-3(2H)-one (3c): :
2-((Z)-4-fluorobenzylidene)-4-((Z)-1-(4-fluorophenyl)-
2-(methylsulfonyl)vinyl)-5-methylfuran-3(2H)-one (3h):
yellow solid (72.4mg, 60%), mp: 179.2–180.3 oC. 1H
NMR (400 MHz, CDCl3) δ 7.82 (dd, J = 8.8, 5.4 Hz, 2H),
7.46–7.40 (m, 2H), 7.16–7.06 (m, 4H), 6.82 (s, 1H), 6.77
(s, 1H), 3.16 (s, 3H), 2.14 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 184.4, 178.6, 164.3 (d, J=251.1), 163.7 (d, J =
251.9), 144.8 (d, J = 2.8 Hz), 142.3 , 133.8 (d, J = 8.6 Hz),
133.3 (d, J = 3.3 Hz), 129.5 (d, J = 8.6 Hz), 129.0 (d, J =
1.3 Hz), 127.9 (d, J = 3.4 Hz), 116.4 (d, J = 7.9 Hz), 116.2
(d, J = 7.8 Hz)., 115.4, 113.3, 42.7, 15.6. HRMS (m/z)
(ESI): calcd for C21H17F2O4S 403.0816 [M+H]+, found
403.0809.
1
yellow oil (95.1 mg, 75%). H NMR (400 MHz, CDCl3) δ
7.75 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.26 (d,
J = 8.1 Hz, 2H), 7.21 (d, J = 8.1 Hz, 2H), 6.85 (s, 1H),
6.82 (s, 1H), 3.15 (s, 3H), 2.71–2.63 (m, 4H), 2.13 (s, 3H),
1.27–1.20 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 184.6,
178.3, 147.6, 147.2, 145.1, 143.6, 134.6, 131.9, 129.2,
128.7, 128.6, 128.2, 127.6, 115.5, 114.5, 42.8, 28.9, 28.6,
15.6, 15.3, 15.2. HRMS (m/z) (ESI): calcd for C25H27O4S
423.1630 [M+H]+, found 423.1621.
5 - m e t h y l - 4 - ( ( Z ) - 2 - ( m e t h y l s u l f o n y l ) - 1 - ( 4 -
propylphenyl)vinyl)-2-((Z)-4-propylbenzylidene)furan-
1
3(2H)-one (3d): yellow oil (87.5 mg, 80%). H NMR (400
MHz, CDCl3) δ 7.75 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8.1
Hz, 2H), 7.26 (s, 2H), 7.20 (d, J = 8.1 Hz, 2H), 6.85 (s,
1H), 6.80 (s, 1H), 3.16 (s, 3H), 2.62 (d, J = 9.5 Hz, 4H),
2.14 (s, 3H), 1.66 (dd, J = 12.3, 7.4 Hz, 4H), 0.94 (d, J =
8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 184.7, 178.4,
146.1, 145.8, 145.1, 143.8, 134.6, 133.3, 131.8, 129.6,
129.4, 129.3, 129.2, 128.1, 127.5, 115.5, 114.6, 42.9, 38.1,
(Z)-5-methyl-4-((E)-2-(methylsulfonyl)-1-(thiophen-2-
yl)vinyl)-2-(thiophen-2-ylmethylene)furan-3(2H)-one
o
1
(3i): brown solid (34.1 mg, 30%), mp: 111.5–113.5 C. H
NMR (400 MHz, CDCl3) δ 7.63 (d, J = 5.1 Hz, 1H), 7.52
(d, J = 3.6 Hz, 1H), 7.46 (dd, J = 5.1, 1.0 Hz, 1H), 7.24 (dd,
J = 3.8, 1.1 Hz, 1H), 7.16–7.12 (m, 2H), 7.07 (dd, J = 5.0,
3.8 Hz, 1H), 6.87 (d, J = 5.2 Hz, 1H), 3.12 (s, 3H), 2.31 (s,
5
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
3H). 13C NMR (100 MHz, CDCl3) δ 183.4, 177.9, 143.6,
140.9, 136.9, 134.8, 134.0, 132.6, 130.1, 129.5, 128.6,
128.1, 125.8, 115.2, 108.3,43.2, 15.6. HRMS (m/z) (ESI):
calcd for C17H15O4S3 379.0132 [M+H]+, found 379.0135.
(Z)-2-benzylidene-4-((Z)-2-((4-chlorophenyl)sulfonyl)-1-
phenylvinyl)-5-methylfuran-3(2H)-one (3o): yellow oil
(122.2 mg, 88%).1H NMR (400 MHz, CDCl3) δ 7.91–7.86
(m, 2H), 7.84 (dd, J = 7.9, 1.5 Hz, 2H), 7.45 (d, J = 8.5 Hz,
5H), 7.40–7.34 (m, 5H), 6.93 (s, 1H), 6.76 (s, 1H), 2.32 (s,
3H). 13C NMR (100MHz, CDCl3) δ 184.2, 178.1, 145.2,
142.8, 140.2, 139.2, 136.5, 131.8, 131.7, 130.9, 130.4,
130.1, 129.5, 129.4, 129.1, 129.0, 1273, 114.79, 113.8,
15.5. HRMS (m/z) (ESI): calcd for C26H20ClO4S 463.0771
[M+H]+; found 463.0769.
(Z)-4-((Z)-3,3-dimethyl-1-(methylsulfonyl)but-1-en-2-
yl)-2-(2,2-dimethylpropylidene)-5-methylfuran-3(2H)-
one (3j): white solid (76.4 mg, 78%), mp: 117.3–118.5 oC.
1H NMR (400 MHz, CDCl3) δ 6.50 (d, J = 1.0 Hz, 1H),
5.91 (d, J = 1.6 Hz, 1H), 2.80 (d, J = 1.4 Hz, 3H), 2.18 (d,
J = 1.4 Hz, 3H), 1.21 (d, J = 1.4 Hz, 9H), 1.08 (d, J = 1.4
Hz, 9H). 13C NMR (100 MHz, CDCl3) δ 185.1, 177.7,
156.5, 145.0, 129.7, 126.5, 112.9, 43.3, 39.6, 32.9, 29.7,
(Z)-2-benzylidene-5-(tert-butyl)-4-((Z)-1-phenyl-2-
tosylvinyl)furan-3(2H)-one (3p): brown solid (128.4 mg,
o
1
28.3, 16.0. HRMS (m/z) (ESI): calcd for C17H27O4S
88%), mp: 170.2–171.8 C. H NMR (400 MHz, CDCl3) δ
7.91 (d, J = 8.6 Hz, 2H), 7.84 (d, J = 7.4 Hz, 2H), 7.47–
7.38 (m, 8H), 7.34 (s, 2H), 6.89 (d, J = 0.8 Hz, 1H), 6.82 (s,
1H), 1.34 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 186.23,
184.29, 144.43, 143.55, 140.20, 139.23, 137.65, 132.12,
131.58, 130.72, 130.22, 129.54, 129.49, 129.09, 129.06,
129.00, 127.08, 113.51, 112.61, 36.21, 27.81. HRMS (m/z)
(ESI): calcd for C29H26ClO4S 505.1240 [M+H]+, found
505.1245.
+
3 2 7 . 1 6 3 0 [ M + H ]
,
f o u n d 3 2 7 . 1 6 3 7 .
(Z)-4-((Z)-1-cyclopropyl-2-(methylsulfonyl)vinyl)-2-
(cyclopropylmethylene)-5-methylfuran-3(2H)-one (3k):
white solid (71.5 mg, 81%), mp: 153.7–154.5 oC. 1H NMR
(400 MHz, CDCl3) δ 6.25 (d, J = 11.8 Hz, 1H), 6.09 (s,
1H), 2.98 (s, 3H), 2.20 (s, 3H), 1.93–1.78 (m, 2H), 1.40–
1.31 (m, 2H), 1.21–1.04 (m, 3H), 0.89–0.81 (m, 2H), 0.78
–0.68 (m, 1H). 13C NMR (100MHz, CDCl3) δ 199.2, 191.8,
172.0, 148.9, 128.6, 128.5, 86.8, 39.9, 26.9, 16.2, 14.5,
13.0, 12.1, 10.3, 10.3. HRMS (m/z) (ESI): calcd for
C15H19O4S 295.1004 [M+H]+, found 295.0997.
(Z)-2-benzylidene-5-(4-chlorophenyl)-4-((Z)-2-
(methylsulfonyl)-1-phenylvinyl)furan-3(2H)-one (3q):
1
yellow oil (58.3 mg, 42%). H NMR (400 MHz, CDCl3) δ
7.90 (dd, J = 8.1, 1.3 Hz, 2H), 7.74–7.71 (m, 2H), 7.51–
7.44 (m, 6H), 7.37–7.33 (m, 4H), 7.01 (s, 1H), 6.99 (s, 1H),
3.18 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 184.6, 171.1,
145.1, 144.1, 139.1, 136.1, 131.9, 131.1, 130.7, 129.7,
129.6, 129.3, 129.2, 127.4, 126.2, 115.4, 114.3, 42.9.
HRMS (m/z) (ESI): calcd for C26H20ClO4S 463.0771
[M+H]+, found 463.0779.
(Z)-2-heptylidene-5-methyl-4-((Z)-1-(methylsulfonyl)
oct-1-en-2-yl)furan-3(2H)-one (3l): white oil (89.5 mg,
78%), H NMR (400 MHz, CDCl3) δ 6.44 (s, 1H), 6.13 (s,
1H), 2.88 (s, 3H), 2.51 (d, J = 7.6 Hz, 2H), 2.23 (s, 3H),
1.63 (d, J = 7.6 Hz, 2H), 1.46 (d, J = 7.6 Hz, 2H), 1.30
(ddd, J = 13.0, 8.1, 4.0 Hz, 14H), 0.88 (d, J = 7.4 Hz, 6H).
13C NMR (100 MHz, CDCl3) δ 177.2, 169.5, 162.6, 152.3,
128.9, 122.7, 112.2, 42.8, 38.4, 33.4, 31.5, 31.4, 28.8, 28.6,
26.6, 26.5, 22.5, 22.4, 18.8, 14.0, 14.0. HRMS (m/z) (ESI):
calcd for C21H34O4S 383.2251 [M+H]+, found 383.2242.
1
1,1'-(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis(3-
phenylprop-2-yn-1-one) (5aa): yellow solid (85.3 mg,
o
1
80%), mp: 174.5–176.3 C. H NMR (400 MHz, CDCl3) δ
9.23 (s, 1H), 9.15 (s, 1H), 7.65 (t, J = 7.2 Hz, 4H), 7.50–
7.46 (m, 2H), 7.39–7.33 (m, 4H), 3.22 (s, 3H), 3.08 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 177.9, 174.8, 144.9,
142.0, 139.6, 136.5, 135.0, 133.6, 133.4 133.3, 131.4,
131.4, 128.8, 119.2, 95.8, 94.9, 88.2, 86.1, 43.8, 17.7.
HRMS (m/z) (ESI): caled for C22H19O4S 427.1004
[M+H]+, found 427.0991.
(Z)-2-benzylidene-5-methyl-4-((Z)-1-phenyl-2-
(phenylsulfonyl)vinyl)furan-3(2H)-one (3m): yellow
solid (106.7 mg, 83%), mp: 158.5–160.1 oC. 1H NMR (400
MHz, CDCl3) δ 7.94 (d, J = 7.7 Hz, 2H), 7.84 (d, J = 7.1
Hz, 2H), 7.58 (s, 1H), 7.52–7.43 (m, 6H), 7.37 (d, J = 4.8
Hz, 4H), 6.98 (s, 1H), 6.73 (s, 1H), 2.35 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 184.3, 178.2, 145.2, 142.4, 140.8,
136.6, 133.5, 131.7, 130.8, 130.7, 130.3, 129.2, 129.1,
129.0, 127.9, 127.2, 114.7, 113.6, 15.6. HRMS (m/z) (ESI):
calcd for C26H21O4S 429.1161 [M+H]+, found 429.1153.
General Experimental Procedure for Synthesis of
sulfonylbenzenes 5.
The mixture of β-keto sulfone 1 (0.25 mmol), alkyne
ketone 4 (0.6 mmol), K2CO3 (0.075 mmol) and DMF (2
mL) was stirred at 70 oC for 30 min. Then the solution was
diluted with water and extracted with ethyl acetate (3 × 30
mL). The combined organic layers were dried with
anhydrous Na2SO4 and concentrated under reduced
pressure. The residue was purified by column
chromatography to give the product 5.
(Z)-2-benzylidene-5-methyl-4-((Z)-1-phenyl-2 tosylvinyl)
furan-3(2H)-one (3n): yellow solid (112.8 mg, 85%), mp:
160.1–161.8 oC. 1H NMR (400 MHz, CDCl3) δ 7.82 (dd, J
= 13.8, 7.5 Hz, 4H), 7.46 (d, J = 7.6 Hz, 3H), 7.37 (dt, J =
8.6, 3.7 Hz, 5H), 7.28 (d, J = 8.1 Hz, 2H), 6.96 (s, 1H),
6.73 (s, 1H), 2.38 (s, 3H), 2.35 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 184.32, 178.03, 145.26, 144.50, 141.70,
136.67, 131.88, 131.62, 131.08, 130.67, 130.26, 129.87,
129.07, 129.02, 128.97, 127.91, 127.19, 113.39, 21.65,
15.52. HRMS (m/z) (ESI): calcd for C27H23O4S 443.1317
[M+H]+, found 443.1312.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)
bis(phenylmethanone) (5a): white solid (77.6 mg, 82%),
o
1
mp: 172.1–174.3 C. H NMR (400 MHz, CDCl3) δ 8.62
(s, 1H), 7.95 (s, 1H), 7.79 (t, J = 8.2 Hz, 4H), 7.63 (dd, J =
14.1, 7.2 Hz, 2H), 7.50 (t, J = 7.4 Hz, 4H), 3.18 (s, 3H),
2.72 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 196.2, 193.8,
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201700830
Advanced Synthesis & Catalysis
142.7, 140.6, 139.8, 136.1, 136.0, 135.8, 134.5, 133.3,
133.0, 131.8, 130.1, 129.9, 129.0, 128.7, 43.8, 17.4.
HRMS (m/z) (ESI): caled for C26H19O4S 379.1004 [M+H]
+, found 379.0997.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((4-
(trifluoromethyl)phenyl)methanone) (5g): yellow oil
(82.3 mg, 64%). 1H NMR (400 MHz, CDCl3) δ 8.62 (d, J =
1.2 Hz, 1H), 7.97 (d, J = 1.2 Hz, 1H), 7.91 (dd, J = 15.2,
8.2 Hz, 4H), 7.79 (d, J = 8.2 Hz, 4H), 3.20 (s, 3H), 2.74 (s,
3H). 13C NMR (100MHz, CDCl3) δ 195.0, 192.5, 142.3,
141.2, 140.9, 139.0, 138.6, 135.8 (q, J = 32.7 Hz), 135.1,
134.8 (q, J = 33.7 Hz), 133.0, 132.3, 130.4, 130.1, 126.2 (q,
J = 3.7 Hz), 125.9 (q, J = 3.7 Hz), 123.4 (q, J =271.1 Hz),
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis(p-
tolylmethanone) (5b): yellow oil (79.3 mg, 78%). 1H
NMR (400 MHz, CDCl3) δ 8.58 (s, 1H), 7.91 (s, 1H), 7.69
(d, J = 6.9 Hz, 4H), 7.29 (d, J = 7.9 Hz, 4H), 3.17 (s, 3H),
2.70 (s, 3H), 2.43 (d, J = 2.7 Hz, 6H). 13C NMR (100 MHz, 123.3 (q, J =271.3 Hz), 43.8, 17.6. HRMS (m/z) (ESI):
CDCl3) δ 195.9, 193.6, 145.8, 144.3, 142.9, 140.3, 139.9,
136.1, 133.5, 133.5, 132.8, 131.6, 130.3, 130.1, 129.7,
129.4, 43.7, 21.8, 21.7, 17.3. HRMS(m/z) (ESI): caled for
C24H23O4S 407.1317 [M+H]+, found 407.1310.
caled for C24H17F6O4S 515.0752 [M+H]+, found 515.0743.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((2-
bromophenyl)methanone) (5h): yellow oil (53.6 mg,
1
40%). H NMR (400 MHz, CDCl3) δ 8.51 (d, J = 1.8 Hz,
1H), 7.97 (d, J = 1.8 Hz, 1H), 7.67–7.61 (m, 2H), 7.56–
7.52 (m, 1H), 7.47–7.41 (m, 3H), 7.41–7.38 (m, 1H), 7.35
(dd, J = 7.4, 1.9 Hz, 1H), 3.17 (s, 3H), 2.91 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 196.1, 193.3, 143.5, 142.1,
141.5, 139.0, 138.8, 134.4, 134.4, 134.3, 133.5, 133.4,
133.3, 132.2, 131.4, 129.5, 127.8, 127.7, 120.9, 119.6,
43.8, 17.7. HRMS (m/z) (ESI): caled for C22H17Br2O4S
536.9194 [M+H]+, found 536.9114.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((4-
ethylphenyl)methanone) (5c): yellow oil (76 mg, 70 %).
1H NMR (400 MHz, CDCl3) δ 8.60 (d, J = 1.7 Hz, 1H),
7.93 (d, J = 1.7 Hz, 1H), 7.72 (d, J = 7.8 Hz, 4H), 7.32 (d,
J = 8.0 Hz, 4H), 3.18 (s, 3H), 2.72 (s, 3H), 1.29 (d, J = 1.9
Hz, 2H), 1.27 (d, J = 2.0 Hz, 2H), 1.26 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ 196.0, 193.6, 151.9, 150.5, 143.0,
140.5, 139.4, 136.2, 133.8, 133.8, 132.9, 131.6, 130.5,
130.3, 128.8, 128.3, 43.8, 29.7, 29.1, 17.4, 15.1, 15.1.
HRMS (m/z) (ESI): caled for C26H27O4S 435.1630
[M+H]+, found 435.1622.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis(o-
tolylmethanone) (5i): yellow oil (68.1 mg, 67%). 1H
NMR (400 MHz, CDCl3) δ 8.61 (s, 1H), 7.91 (s, 1H), 7.62
(d, J = 15.1 Hz, 2H), 7.54 (t, J = 6.5 Hz, 2H), 7.46–7.36
(m, 4H), 3.18 (s, 3H), 2.72 (s, 3H), 2.41 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ 196.50, 194.13, 142.81, 140.57,
139.73, 139.08, 138.77, 136.25, 136.1, 136.0, 135.4, 134.2,
133.0, 131.8, 130.4, 128.9, 128.5, 127.7, 127.3, 43.8, 21.4,
21.4, 17.4. HRMS (m/z) (ESI): caled for C24H23O4S
407.1317 [M+H]+, found 407.1310.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((4-(tert-
butyl)phenyl)methanone) (5d): yellow oil (78.5 mg,
1
64%). H NMR (400 MHz, CDCl3) δ 8.61 (d, J = 1.7 Hz,
1H), 7.94 (d, J = 1.7 Hz, 1H), 7.74 (dd, J = 8.4, 1.4 Hz,
4H), 7.51 (d, J = 8.3 Hz, 4H), 3.19 (s, 3H), 2.73 (s, 3H),
1.35 (d, J = 1.7 Hz, 18H). 13C NMR (100 MHz, CDCl3) δ
195.9, 193.5, 158.6, 157.3, 142.9, 140.4, 139.5, 136.1,
1335, 133.5, 133.0, 131.6, 130.2, 130.0, 126.0, 125.7, 43.8,
35.3, 35.2, 31.0, 31.0, 17.3. HRMS (m/z) (ESI): caled for
C30H35O4S 491.2256 [M+H]+, found 491.1906.
(4-methyl-5-(methylsulfonyl)-1,3- phenylene)bis
(naphthalen-2-ylmethanone) (5j) : yellow solid (83.7 mg,
1
70%), mp: 183.3–186.1oC. H NMR (400 MHz, CDCl3) δ
8.74 (s, 1H), 8.26 (s, 1H), 8.17 (s, 1H), 8.07–8.00 (m, 2H),
7.98–7.86 (m, 7H), 7.67–7.52 (m, 4H), 3.22 (s, 3H), 2.79
(s, 3H). 13C NMR (100 MHz, CDCl3) δ 196.2, 193.9,
142.8, 140.8, 139.9, 136.1, 135.5, 133.4, 133.4, 133.3,
133.1, 132.3, 132.2, 132.1, 131.9, 129.8, 129.5, 129.5,
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((4-
fluorophenyl)methanone) (5e): yellow solid (74.6 mg,
1
72%), mp: 165.0–168.1oC. H NMR (400 MHz, CDCl3) δ
8.56 (d, J = 1.5 Hz, 1H), 7.91 (d, J = 1.5 Hz, 1H), 7.85–
7.79 (m, 4H), 7.20–7.15 (m, 4H), 3.18 (s, 3H), 2.71 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 194.5, 192.2, 166.5 (d, 129.2, 128.9, 128.8, 127.9, 127.8, 127.3, 127.1, 125.2,
J = 256.7), 165.8 (d, J = 254.6), 142.5, 140.7, 139.8, 135.7,
132.9 (d, J = 9.7 Hz), 132.7, 132.6 (d, J = 9.4 Hz),132.4 (d,
J = 2.9 Hz), 132.3 (d, J = 3.0 Hz), 131.7, 116.4 (d, J = 22.1
Hz), 116.0 (d, J = 22.1 Hz), 43.7, 17.4. HRMS (m/z)
(ESI): caled for C22H17F2O4S 415.0816 [M+H]+, found
415.0809.
124.3, 43.8, 17.4. HRMS (m/z) (ESI): caled for C30H23O4S
479.1317 [M+H]+, found 479.1303.
1 , 1 ' - ( 4 - m e t h y l - 5 - ( m e t h y l s u l f o n y l ) - 1 , 3 -
phenylene)bis(heptan-1-one) (5l): yellow oil (74.0 mg,
1
75%). H NMR (400 MHz, CDCl3) δ 8.67 (d, J = 1.7 Hz,
1H), 8.21 (d, J = 1.7 Hz, 1H), 3.15 (s, 3H), 3.00 (t, J = 7.3
Hz, 2H), 2.88 (t, J = 7.4 Hz, 2H), 2.77 (s, 3H), 1.76–1.67
(m, 4H), 1.39–1.29 (m, 12H), 0.89 (dd, J = 7.0, 5.5 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 204.8, 197.94, 143.8,
141.0, 140.4, 135.1, 130.4, 130.2, 43.7, 43.2, 38.6, 31.6,
31.5, 28.8, 28.8, 23.9, 23.8, 22.5, 22.4, 17.2, 14.0, 14.0.
HRMS (m/z) (ESI): caled for C22H35O4S 395.2256
[M+H]+, found 395.2248.
(4-methyl-5-(methylsulfonyl)-1,3-phenylene)bis((4-
chlorophenyl)methanone) (5f) : yellow solid (67.1 mg,
o
1
60%), mp: 130.9–132.5 C. H NMR (400 MHz, CDCl3) δ
8.59 (d, J = 1.8 Hz, 1H), 7.92 (d, J = 1.8 Hz, 1H), 7.77 –
7.71 (m, 4H), 7.50 (ddd, J = 6.8, 3.9, 1.8 Hz, 4H), 3.19 (s,
3H), 2.72 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 194.9,
192.5, 142.4, 141.4, 140.9, 140.1, 140.1, 135.6, 134.4,
134.3, 132.8, 131.9, 131.5, 131.3, 129.5, 129.2, 43.8, 17.5.
HRMS (m/z) (ESI): caled for C22H17Cl2O4S 447.0225
[M+H]+, found 447.0218.
(4-methyl-5-(methylsulfonyl)-1, 3-phenylene)
bis(cyclopropylmethanone) (5m): white solid (55.9 mg,
o
1
73%), mp: 180.1–182.3 C. H NMR (400 MHz, CDCl3) δ
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201700830
Advanced Synthesis & Catalysis
8.81 (d, J = 1.8 Hz, 1H), 8.36 (d, J = 1.8 Hz, 1H), 3.17 (s,
3H), 2.83 (s, 3H), 2.71 (s, 1H), 2.35 (s, 1H), 1.39–1.34 (m,
2H), 1.33–1.28 (m, 2H), 1.17 (ddd, J = 13.4, 7.5, 3.7 Hz,
4H). 13C NMR (100 MHz, CDCl3) δ 204.7, 198.3, 144.5,
140.8, 139.9 136.1, 131.0, 130.3, 43.8, 22.1, 17.4, 17.3,
13.4, 12.7. HRMS (m/z) (ESI): caled for C26H19O4S
307.0999 [M+H] +, found 307.0988.
248.8 Hz), 143.3, 140.9, 140.8 (d, J = 1.9 Hz), 137.8,
136.3, 136.0, 135.6 (d, J = 8.0 Hz), 133.9, 133.5, 132.8,
131.0, 130.0, 129.7, 129.3 (d, J = 8.3 Hz), 128.8, 128.5,
126.7 (d, J = 3.2 Hz), 118.4 (d, J = 22.9 Hz), 116.2 (d, J =
20.9 Hz), 43.7. HRMS (m/z) (ESI): caled for C27H20FO4S
459.1066 [M+H]+, found 459.1059.
(6-tosyl-[1,1'-biphenyl]-2,4-diyl)bis(phenylmethanone)
1
(5u): yellow oil (90.4 mg, 70%). H NMR (400 MHz,
(4-methyl-5-(phenylsulfonyl)-1,3-phenylene)
bis(phenylmethanone) (5p): yellow oil (79.3 mg, 72%).
1H NMR (400 MHz, CDCl3) δ 8.77 (s, 1H), 7.92–7.88 (m,
3H), 7.80 (d, J = 7.5 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H),
7.65–7.61 (m, 3H), 7.50 (dd, J = 13.1, 5.6 Hz, 6H), 2.44 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 196.2, 193.9, 142.6,
141.0, 140.2, 140.1, 136.3, 136.1, 135.6, 134.4, 133.7,
133.3, 133.0, 131.8, 130.1, 129.9, 129.3, 128.9, 128.8,
128.7, 128.6, 127.9, 127.9, 17.3. HRMS (m/z) (ESI): caled
for C27H21O4S 441.1161 [M+H]+, found 441.1155.
CDCl3) δ 8.98 (d, J = 1.8 Hz, 1H), 8.06 (d, J = 1.8 Hz, 1H),
7.91–7.88 (m, 2H), 7.65 (dd, J = 10.6, 4.2 Hz, 1H), 7.57 –
7.52 (m, 2H), 7.44 (dd, J = 5.8, 4.5 Hz, 3H), 7.26 (dd, J =
9.8, 5.5 Hz, 2H), 7.08 (dd, J = 14.0, 7.9 Hz, 3H), 6.96 (dd,
J = 14.7, 6.5 Hz, 4H), 6.83–6.78 (m, 2H), 2.31 (s, 3H). 13
C
NMR (100 MHz, CDCl3) δ 196.1, 194.0, 144.1, 143.6,
143.0, 141.7, 137.0, 137.0, 136.5, 136.3, 133.6, 133.4,
133.2, 132.4, 131.0, 130.9, 130.1, 129.5, 129.2, 128.8,
128.3, 128.3, 127.9, 127.0, 21.6. HRMS (m/z) (ESI): caled
for C33H25O4S 517.1474 [M+H]+, found 517.1465.
(4-methyl-5-tosyl-1,3-phenylene)bis(phenylmethanone)
1
(5q): yellow oil (85.2 mg, 75%). H NMR (400 MHz,
( 6 - ( p h e n y l s u l f o n y l ) - [ 1 , 1 ' - b i p h e n y l ] - 2 , 4 -
CDCl3) δ 8.74 (d, J = 1.5 Hz, 1H), 7.91 (d, J = 1.5 Hz,
1H), 7.81–7.73 (m, 6H), 7.66–7.60 (m, 2H), 7.48 (dd, J =
16.5, 8.6 Hz, 4H), 7.34 (d, J = 8.1 Hz, 2H), 2.44 (d, J = 2.8
Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 196.3, 194.0,
144.9, 142.5, 141.3, 140.1, 137.1, 136.3, 136.1, 135.4,
134.4, 133.3, 132.8, 131.7, 130.1, 130.0, 130.0, 128.9,
128.7, 128.0, 21.6, 17.3. HRMS (m/z) (ESI): caled for
C28H23O4S 455.1317 [M+H]+, found 455.1311.
diyl)bis(phenylmethanone) (5v): yellow oil (94.2 mg,
58%). H NMR (400 MHz, CDCl3) δ 9.10 (d, J = 1.8 Hz,
1
1H), 8.16 (t, J = 3.7 Hz, 1H), 8.02–7.97 (m, 2H), 7.78–
7.73 (m, 1H), 7.68–7.63 (m, 2H), 7.57–7.44 (m, 5H), 7.38
–7.30 (m, 3H), 7.28–7.26 (m, 2H), 7.20–7.15 (m, 1H), 7.01
(dd, J = 10.7, 4.9 Hz, 2H), 6.90–6.82 (m, 2H). 13C NMR
(100MHz, CDCl3) δ 196.1, 194.0, 143.6, 143.0, 141.3,
139.9, 137.1, 136.5, 136.2, 133.6, 133.5, 133.1, 133.0,
132.6, 131.1, 130.9, 130.1, 129.5, 128.9, 128.6, 128.3,
128.3, 127.8, 127.0. HRMS (m/z) (ESI): caled for
C33H23O4S 503.1317 [M+H]+, found 503.1307.
(5-((4-chlorophenyl)sulfonyl) -4-methyl-1,3-
phenylene)bis(phenylmethanone) (5r): yellow oil (65.3
1
mg, 55%). H NMR (400 MHz, CDCl3) δ 8.77 (d, J = 1.8
Hz, 1H), 8.42 (s, 1H), 7.95 (d, J = 1.8 Hz, 1H), 7.87 – 7.85
(m, 3H), 7.83 (dd, J = 4.4, 3.8 Hz, 2H), 7.77 (dd, J = 8.4,
1.3 Hz, 2H), 7.65 (dd, J = 6.9, 1.4 Hz, 2H), 7.54 (s, 4H),
2.47 (s, 3H). 13C NMR (100MHz, CDCl3) δ 196.0, 194.0,
143.6, 141.3, 139.9, 137.1, 136.5, 136.2, 133.6, 133.5,
133.0, 132.6, 130.9, 130.1, 129.5, 128.9, 128.6, 128.3,
127.8, 127.0, 29.7. HRMS (m/z) (ESI): caled for
C27H20ClO4S 475.0771 [M+H]+, found 475.0760.
(E)-1,1'-(5-benzylidene-4-oxo-2-phenylcyclopent-2-ene-
1,1-diyl)diethanone (7da): yellow oil (79.3 mg, 82%). H
1
NMR (400 MHz, CDCl3): δ 7.81 (s, 1H), 7.67 (d, J = 7.0
Hz, 2H), 7.55 (d, J = 3.2 Hz, 2H), 7.48–7.43 (m, 6H), 7.20
(s, 1H), 1.99 (s, 6H). 13C NMR (100 MHz, CDCl3): δ
199.5, 195.2, 166.9, 138.0, 132.7, 132.2, 132.0, 132.0,
131.8, 131.4, 131.1, 129.4, 129.0, 128.5, 76.36, 27.19.
HRMS (m/z) (ESI): calcd for C22H19O3 331.1334 [M+H]+,
found 331.1326.
(4'-chloro-6-(methylsulfonyl)-[1,1'-biphenyl]- 2,4 diyl)
bis(phenylmethanone) (5s): yellow oil (85.5 mg, 72%).
1H NMR (400 MHz, CDCl3) δ 8.57 (d, J = 1.7 Hz, 1H),
7.90 (d, J = 1.7 Hz, 1H), 7.67–7.62 (m, 2H), 7.44 (d, J =
7.4 Hz, 1H), 7.35–7.29 (m, 5H), 7.14 (t, J = 7.8 Hz, 2H),
7.06–7.00 (m, 4H), 2.48 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 195.5, 193.6, 143.4, 141.1, 140.9, 137.6, 136.2,
135.9, 135.4, 134.0, 133.5, 132.7, 132.2, 131.9, 130.9,
130.0, 129.6, 128.8, 128.5, 127.9, 43.6. HRMS (m/z)
(ESI): caled for C27H20ClO4S 475.0771 [M+H]+, found
475.0764.
(E)-ethyl 1-acetyl-5-benzylidene-4-oxo-2-phenyl
cyclopent-2-enecarboxylate (7ea): yellow oil (81.09 mg,
75%). H NMR (400 MHz, CDCl3): δ 7.71 (s, 1H), 7.65
1
(ddd, J = 10.0, 5.9, 2.3 Hz, 4H), 7.43–7.39 (m, 6H), 7.09 (s,
1H), 4.02 (dd, J = 7.1, 0.8 Hz, 2H), 1.94 (s, 3H), 0.91 (t, J
= 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 199.62,
194.82, 166.75, 166.47, 136.77, 132.93, 132.32, 131.96,
131.58, 131.55, 130.90, 129.01, 128.68, 128.43, 77.44,
77.12, 76.81, 71.40, 62.09, 26.32, 13.53. HRMS (m/z)
(ESI): calcd for C23H21O4 361.1440 [M+H]+, found
361.1432.
(3'-fluoro-6-(methylsulfonyl)-[1,1'-biphenyl]-2,4-
diyl)bis(phenylmethanone) (5t): yellow solid (71.1 mg,
62%), mp: 198.5-199.9. H NMR (400 MHz, CDCl3) δ
“CCDC for compound 3c: 1525701 and for compound 7ea:
1548541 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge
from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.”
1
8.78 (d, J = 1.7 Hz, 1H), 8.11 (d, J = 1.7 Hz, 1H), 7.88–
7.84 (m, 2H), 7.65 (t, J = 7.4 Hz, 1H), 7.57–7.49 (m, 5H),
7.34 (t, J = 7.7 Hz, 2H), 7.21 (td, J = 7.9, 5.9 Hz, 1H), 7.10
–7.02 (m, 2H), 6.97 (td, J = 8.5, 1.9 Hz, 1H), 2.70 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 195.5, 193.6, 161.6 (d, J =
8
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10.1002/adsc.201700830
Advanced Synthesis & Catalysis
Acknowledgements
[11] a) S. Kiren, A. Padwa, J. Org. Chem. 2009, 74, 7781;
b) J. Alemán, V. Marcos, L. Marzo, J. L. García
Ruano, Eur. J. Org. Chem. 2010, 4482; c) O. Garcia
Mancheno, P. Tangen, R. Rohlmann, R. Froehlich, J.
Aleman, Chem. Eur. J. 2011, 17, 984; d) J. Deng, F.
Wang, W. Yan, J. Zhu, H. Jiang, W. Wang, J. Li,
Chem Commun. 2012, 48,148; e) Q. G. Wang, Q. Q.
Zhou, J. G. Deng, Y. C. Chen, Org. Lett. 2013, 15,
4786.
[12] N.T. Patil, I. Kadota, A Shibuya, Y. S. Gyoung, Y.
Yamamoto, Adv. Synth. Catal. 2004, 346, 800.
[13] Y. Kuninobu, H. Matsuzaki, M. Nishi, K. Takai, Org.
Lett. 2011, 13, 2959.
[14] Y. He, Y. Y. Xie, Y. C. Wang, X. M. Bin, D. C. Hu,
H. S. Wang, Y. M. Pan, RSC. Adv. 2016, 6, 58988-
58993.
[15] Q. H. Teng, Y. L. Xu, Y. Liang, H. S. Wang, Y. C.
Wang, Y. M. Pan, Adv. Synth. Catal. 2016, 358, 1897.
[16] Y. L. Xu, Q. H. Teng, W. Tong, H. S. Wang, Y. M.
Pan, X. L. Ma, Molecules. 2017, 22, 109.
[17] a) S. Y. Woo, J. H. Kim, M. K. Moon, S. H. Han, S. K.
Yeon, J. W. Choi, B. K. Jang, H. J. Song, Y. G. Kang,
J. W. Kim, J. Lee, D. J. Kim, O. Hwang, K. D. Park, J.
Med. Chem. 2014, 57, 1473; b) E. Dunny, W. Doherty,
P. Evans, J. P. G. Malthouse, D. Nolan, A. Knox, J.
Med. Chem. 2013, 56, 6638; c) D. C. Meadows, J.
Gervay-Hague, Med. Res. Rev. 2006, 26, 793.
[18] a) H. T. Sakamoto, D. Flausino, E. E. Castellano, C. B.
W. Stark, P. J. Gates, N. P. Lopes, J. Nat. Prod. 2003,
66, 693; b) V. L. Goncalves de Moraes, V. M.
Rumjanek, J. B. Calixto, Eur. J. Pharmacol. 1996,
312, 333; c) M. Togashi, S. Ozawa, S. Abe, T.
Nishimura, M. Tsuruga, K. Ando, G. Tamura, S.
Kuwahara, M. Ubukata, J. Magae, J. Med. Chem.
2003, 46, 4113; d) S. S. Shin, Y. Byun, K. M. Lim, J.
K. Choi, K.-W. Lee, J. H. Moh, J. K. Kim, Y. S.
Jeong, J. Y. Kim, Y. H. Choi, H.-J. Koh, Y. -H. Park,
Y. I. Oh, M. -S. Noh, S. Chung, J. Med. Chem. 2004,
47, 792.
We would like to thank the National Natural Science Foundation
of China (21362002 and 81260472), the Guangxi Natural
Science Foundation of China (2014GXNSFDA118007,
2016GXNSFEA380009 and 2016GXNSFGA380005), the State
Key Laboratory for Chemistry and Molecular Engineering of
Medicinal Resources (CMEMR2014-A02 and CMEMR2012-A20)
and Guangxi’s Medicine Talented Persons Small Highland
Foundation (1306) for financial support.
References
[1] a) M. Petrini, Chem. Rev. 2005, 105, 3949; b) T. G.
Back, K. N. Clary, D. Gao, Chem. Rev. 2010, 110,
4498; c) J.-E. Bäckvall, R. Chinchilla, C. Nájera, M.
Yus, Chem. Rev. 1998, 98, 2291; d) A. N. R. Alba, X.
Companyó, R. Rios, Chem. Soc. Rev. 2010, 39, 2018.
[2] a) S. F. Barbuceanu, G. L. Almajan, I. Saramet, C.
Draghici, A. I. Tarcomnicu, G. Bancescu, Eur. J. Med.
Chem. 2009, 44, 4752; b) M. Artico, R. Silvestri, E.
Pagnozzi, B. Bruno, E. Novellino, G. Greco, S. Massa,
A. Ettorre, A. Giulia Loi, F. Scintu, P. La Colla, J. Med.
Chem. 2000, 43, 1886; c) V. Padmavathi, P. Thriveni,
G. S. Reddy, D. Deepti, Eur. J. Med. Chem. 2008, 43,
917; d) Z.-H. Wen, C.-H. Chao, M.-H. Wu, J.-H. Sheu,
Eur. J. Med. Chem. 2010, 45, 5998; e) C. R. Lee, J. A.
Balfour, Drug. 1994, 48, 907; f) L. A. Taylor, J. W.
Clader, Bioorg. Med. Chem. Lett. 2000, 10, 2209.
[3] Y. M. Markitanov, V. M. Timoshenko, Y. G.
Shermolovich, J. Sulfur. Chem. 2014, 35, 188.
[4] a) M. Julia, J. M. Paris, Tetrahedron Lett. 1973, 14,
4833; b) T. Mandai, T. Yanagi, K. Araki, Y. Morisaki,
M. Kawada, J. Otera, J. Am. Chem. Soc. 1984, 106,
3670; c) G. Pandey, J. Vaitla, Org. Lett. 2015, 17, 4890.
[5] M. Nielsen, C. B. Jacobsen, M. W. Paixao, N. Holub,
K. A. Jørgensen, J. Am. Chem. Soc. 2009, 131, 10581.
[6] A. Kumar, S. Sharma, V. D. Tripathi, S. Srivastava,
Tetrahedron. 2010, 66, 9445.
[19] a) X. Cheng, Y. Zhou, F. Zhang, K. Zhu, Y.Liu, Y. Li,
Chem. Eur. J. 2016, 22, 12655; b) Q. Yao, L. Kong, F.
Zhang, X. Tao, Y. Li, Adv. Synth. Catal. 2017, DOI:
10.1002/adsc.201700565; c) M. Murai, M. Nakamura,
K. Takai, Org. Lett. 2014, 16, 5784; d) Y. Kuninobu,
A. Kawata, M. Nishi, S. Yudha, J. Chen, K. Takai,
Chem. Asian J. 2009, 4, 1424.
[7] C. Curti, M. D. Crozet, P. Vanelle, Tetrahedron, 2009,
65, 200.
[8] M. T. Saraiva, G. P. Costa, N. Seus, R. F. Schumacher,
G. Perin, M. W. Paixão, R. Luque, D. Alves, Org. let.
2015, 17, 6206.
[9] M. Y. Chang, Y. C. Cheng, Y. J. Lu, Org. Lett. 2014,
16, 6252.
[10] J. L. Marco, J. Org. Chem. 1997, 62, 6575.
[20] Q. F. Zhou, F. Yang, Q. X. Guo, S. Xue, Synlett. 2007,
2073.
9
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Advanced Synthesis & Catalysis
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