Oxidation of Aryl Sulfides to Sulfones with Alumina-Supported Ruthenium Catalyst in Dimethyl Carbonate-Water Media

Article abstract of DOI:10.1055/s-0035-1560834

A new procedure for the oxidation of sulfides to sulfones utilizing heterogeneous ruthenium reagent has been developed. A small amount of ruthenium trichloride (RuCl₃) supported on alumina and excess sodium metaperiodate (NaIO₄) was used to produce the ruthenium oxidizing catalyst in the reaction mixture. Sodium metaperiodate oxidized the pre-catalyst RuCl₃ to RuO₄ and also maintained a constant supply of RuO₄ by oxidizing lower valent ruthenium ions during the course of the reaction. An environmentally friendly solvent mixture of dimethyl carbonate (DMC) and water was employed. A wide variety of aromatic sulfides were oxidized to sulfones in good to excellent yields by utilizing this procedure.

Full text of DOI:10.1055/s-0035-1560834

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2016, 48, 429–436
paper
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M. H. Ali et al.
Paper
Synthesis
Oxidation of Aryl Sulfides to Sulfones with Alumina-Supported
Ruthenium Catalyst in Dimethyl Carbonate–Water Media
Mohammed Hashmat Ali*a
Bjorn Olesena
Brindaban Ranub
Luke Clipparda
Jacqueline Heatha
Garrett Meyera
alumina-supported RuCl3 + NaIO4
O
O
DMC–H2O
S
S
R1
R2
R1
R2
1–3 h
yields 58–98%
R1, R2 = alkyl, aryl
Tawanika Williamsa
a Chemistry Department, Southeast Missouri State University,
Cape Girardeau, Missouri 63701, USA
mhali@semo.edu
b Indian Association for the Cultivation of Science, Jadavpur,
Kolkata 700 032, India
Received: 02.08.2015
Accepted after revision: 06.10.2015
Published online: 03.12.2015
disulfates,10 hypochlorites,10–13 N-bromo salts,14 hyperva-
lent iodine compounds,15 peroxides,10,11,16–19 peracids,20,21
oxygen or air,22–26 bromamine-T,27,28 oxone,10,11,29,30 N-oxide
componds,31,32 periodic acid,33,34 and periodates10,35–52 ef-
fectively convert lower valent ruthenium compounds into
RuO4. Introduction of a co-oxidant makes it possible to use
ruthenium in organic transformations more economically.
Given that RuO4 is a very powerful oxidant, selectivity in
ruthenium-promoted oxidation reactions is often an issue.
To improve selectivity and yield, a number of modifications
to the original RuO4-promoted reaction have been reported.
These include oxidation reactions under phase-transfer
conditions,48–50 under solvent-free ultrasonic radiation,51
and through the use of Ru–Ce bimetallic oxidant.52
DOI: 10.1055/s-0035-1560834; Art ID: ss-2015-m0253-op
Abstract A new procedure for the oxidation of sulfides to sulfones uti-
lizing heterogeneous ruthenium reagent has been developed. A small
amount of ruthenium trichloride (RuCl3) supported on alumina and ex-
cess sodium metaperiodate (NaIO4) was used to produce the rutheni-
um oxidizing catalyst in the reaction mixture. Sodium metaperiodate
oxidized the pre-catalyst RuCl3 to RuO4 and also maintained a constant
supply of RuO4 by oxidizing lower valent ruthenium ions during the
course of the reaction. An environmentally friendly solvent mixture of
dimethyl carbonate (DMC) and water was employed. A wide variety of
aromatic sulfides were oxidized to sulfones in good to excellent yields
by utilizing this procedure.
Key words sulfides, sulfones, RuO4, dimethyl carbonate, green chem-
In terms of environmental benefits, heterogeneous
rather than homogeneous reactions are generally a better
choice. Heterogeneous reagents are more environmentally
friendly than homogeneous reagents, and a solid support
renders heterogeneous reagents safer by anchoring them
and not allowing them to become airborne. Furthermore,
heterogeneous reagents generate less waste and often re-
duce reaction times by spreading reagents on the large sur-
face area provided by the solid substrate particles. In gener-
al, heterogeneous systems also allow reactions to be carried
out in a safer manner.
As an extension of our interest in developing green pro-
cedures for the transformation of organic functional
groups,53–58 we became interested in the possibility of de-
veloping a simple, effective, and environmentally friendly
heterogeneous ruthenium reagent for sulfide oxidation in
biodegradable dimethyl carbonate reaction media.
istry
Since Djerassi and Engle introduced ruthenium tetrox-
ide (RuO4) as an oxidizing reagent in 1953, the chemistry of
RuO4-promoted oxidation reactions has expanded greatly1–6
to the point where RuO4 is now a commonly used, versatile
oxidizing reagent. Oxidation of C–H bonds of saturated hy-
drocarbons, oxygen transfer to alkenes in epoxidation, di-
hydroxylation, ketohydroxylation, cleavage of carbon–car-
bon and carbon–heteroatom multiple bonds, oxidation of
aromatic compounds, oxidation of a carbon adjacent to a
heteroatom such as alcohol oxidation, and oxidation of het-
eroatoms have all been successfully carried out with
RuO4.3,4 RuO4 can be used as either a stoichiometric or a cat-
alytic reagent. However, since RuO4 is expensive, most often
a small amount of RuCl3 or RuO2 is used to generate RuO4
and the reduced form of the ruthenium produced in the re-
action is re-oxidized with a less expensive co-oxidant. A
wide variety of oxidants are capable of re-oxidizing lower
valent ruthenium compounds such as RuCl3 and RuO2 to
RuO4. Trichloroisocyanuric acid,7 bromate salts,8–10 peroxy-
Ruthenium reagents anchored on solids using linkers
have been reported.59–69 Linkers are generally attached to
solids using multistep procedures. However, these prepara-
tive methods are not as environmentally friendly as de-
sired. Cheung reported the preparation of a heterogeneous
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M. H. Ali et al.
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ruthenium reagent by impregnating [(1,4,7-trimethyl-
1,4,7-triazacyclononane)Ru(CF3COO)2(H2O)]CF3COO– com-
plex on silica gel for the oxidation of secondary alcohols to
ketones and for the epoxidation of alkenes using tert-butyl
hydroperoxide (TBHP) as the stoichiometric oxidant.59
Preparation of this ruthenium complex involves multiple
steps and requires expensive and/or corrosive reagents
such as silver trifluoromethane sulfonate and trifluoroace-
tic acid. RuO2 supported on V2O5-Al2O3,60 TiO2,61,69 zeo-
lite,62,63 Al2O3,64,65,67 hydroxyapatite,66 and ZSM-568 have
also been used in the oxidation of various functional
groups. RuO2 on V2O5-Al2O3 was used in the oxidation of cy-
clohexane and alkenes with peroxide as co-oxidant. This re-
agent produced low to moderate yield of the products.60
RuO2 on zeolite was also found to be active towards cyclo-
hexane oxidation.62 Ruthenium reagents on Al2O3, zeolite,
hydroxylapatite, and ZSM-5 were found to be effective in
aerobic oxidation of alcohols.63,64,66,68 Alumina-supported
ruthenium reagents oxidize primary amines to nitriles and
secondary amines to imines in the presence of dioxy-
gen.65,67
Our interest in green chemistry prompted us to investi-
gate the use of solid-supported ruthenium reagents in
DMC–H2O media. Oxidation of diphenyl sulfide was ex-
plored as the model reaction, and the results obtained un-
der various conditions are reported in Table 1. We found
that both Ru/Al2O3 and Ru/SiO2 are capable of oxidizing di-
phenyl sulfide to diphenyl sulfone in aqueous media, albeit
in lower yield and requiring longer reaction time (entries
1–5). We believe that the limited solubility of diphenyl sul-
fide in water led to the lower yields in this reaction. Ru/SiO2
and Ru/Al2O3 reactions in water for 24 hours produced 42
and 10% yields of diphenyl sulfones respectively (entries 1
and 4). Yields improved to 81 and 44%, respectively, when
these reactions were allowed to continue for 48 hours (en-
tries 2 and 5). However, ruthenium on Al2O3 in DMC–H2O
produced 96% yield of product in just one hour (entry 6),
and ruthenium on SiO2 under a similar conditions produced
75% yield of product in three hours (entry 7). Ruthenium on
Al2O3 produced lower yield when the reaction time was
shorter than one hour (entry 8). The use of either RuCl3
alone on silica gel (entry 3) or FeCl3 instead of NaIO4 as co-
oxidant (entry 9), failed to produce the oxidation product.
RuO4-promoted reactions generally employ water–halo-
genated hydrocarbon biphasic media. The role of the organ-
ic solvent in the biphasic media is to dissolve organic sub-
strates and water is necessary because the stoichiometric
oxidants usually have low solubility in organic solvents.
Low-valent ruthenium compounds are also insoluble in
most organic solvents. Historically, CCl4–H2O has been used
in RuO4-promoted reactions because this biphasic media
produced better yields of product. Recently, biphasic media
of water and nonhalogenated solvents, such as, acetoni-
trile–water,70 acetonitrile–hexane–water,71 ethyl acetate–
water,50,72,73 ethyl acetate–acetonitrile–water,8–11,74–79 cyclo-
Table 1 Standardization of Reaction Conditions for the Oxidation of
Diphenyl Sulfide with γ-Alumina-Supported Ruthenium Catalyst
catalyst, solvent
O
O
r.t., time
S
S
Ph
Ph
Ph
Ph
(1 mmol)
catalyst: Ru (0.0005 mmol) + co-catalyst (3 mmol)
Entry Catalyst Co-oxidant Solvent
Time (h) Yield (%)a
1
2
3
4
5
6
7
8
9
Ru/SiO2
Ru/SiO2
Ru/SiO2
Ru/Al2O3
Ru/Al2O3
Ru/Al2O3
Ru/SiO2
Ru/Al2O3
Ru/Al2O3
NaIO4
NaIO4
–
H2O
24
48
24
24
48
1
42
81
0
hexane–acetonitrile–water,75
acetone–acetonitrile–wa-
H2O
ter,75 and dimethyl carbonate–water80 were found to work
well in ruthenium-promoted oxidation reactions. Dimethyl
carbonate (DMC) is a biodegradable solvent and has very
low or no toxicity.81–82 It has received federal VOC exemp-
tion in 2009 in the USA. Introduction of DMC in the ruthe-
nium oxidation procedure is thus a step closer toward de-
veloping a green reaction.
H2O
NaIO4
NaIO4
NaIO4
NaIO4
NaIO4
FeCl3
H2O
10
44
96
75
57
0
H2O
DMC–H2O (8:1)
DMC–H2O (8:1)
DMC–H2O (8:1)
DMC–H2O (8:1)
3
0.5
12
We report herein a heterogeneous procedure for the ox-
idation of sulfides with RuCl3 and NaIO4 using DMC–H2O
media (Scheme 1). This procedure can be used to oxidize
sulfides carrying various functional groups and offers sev-
eral benefits of green chemistry.
a Yield of purified product.
Given that the use of ruthenium on Al2O3 in DMC–H2O
produced the best results in our model study (Table 1, entry
6), we used these reaction conditions for the oxidation of a
wide variety of sulfides; the results are presented in Table
2.
A large number of aromatic sulfides were oxidized by
using our newly developed procedure. The presence of acti-
vating groups (Table 2, entries 9, 11, and 13) or deactivating
groups (entries 3, 5–8, 10, 14, and 15) did not affect the re-
action time or yields significantly. The results indicate that
alumina-supported RuCl3 + NaIO4
O
O
DMC–H2O
S
S
R1
R2
R1
R2
1–3 h
yields 58–98%
R1, R2 = alkyl, aryl
Scheme 1 General reaction scheme for oxidation of sulfides to sul-
fones with alumina-supported ruthenium catalyst
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M. H. Ali et al.
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a large number of functional groups can tolerate the reac-
tion conditions. The survival of nitrile (entry 3), nitro (en-
try 6), ketone (entries 7 and 17), aldehyde (entry 8), ester
(entry 10), methoxy group (entries 11 and 13), and hetero
aromatics (entries 9 and 17) is significant. Aromatic rings
also survived during these reactions. Notably, aromatic
compounds are known to undergo oxidation with rutheni-
um reagents.33,78 The use of thiazole produced a brown tar
that we were unable to purify (entry 18).
Table 2 Oxidation of Aryl Sulfides to the Corresponding Sulfones Using γ-Alumina-Supported Ruthenium Catalyst
alumina-supported RuCl3 + NaIO4
DMC–H2O
O
O
S
R1
R2
S
R1
R2
Entry
1
Sulfide
Time (h)
1
Sulfone
Yield (%)a
91
O
O
O
S
S
S
Me
Me
O
S
2
3
4
5
2
2
2
2
96
98
78
82
O
O
S
S
CN
Cl
CN
Cl
O
O
O
S
S
O
O
S
S
F
S
S
F
Cl
Cl
Cl
Cl
O
6
7
8
2
3
2
96
71
95
NO2
NO2
O
O
O
O
O
S
S
S
S
Cl
COMe
CHO
Cl
COMe
CHO
Cl
N
Cl
N
O
S
S
9
2
97
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Table 2 (continued)
Entry
Sulfide
Time (h)
1.5
Sulfone
Yield (%)a
O
O
O
O
S
S
10
78
97
Br
COOEt
Br
COOEt
O
S
S
11
12
1
1
OMe
OMe
O
S
S
64
Cl
Cl
OMe
OMe
O
O
S
S
13
14
2
1
89
91
OMe
OMe
S
O
S
O
Cl
Br
Br
Cl
Br
Br
NO2
NO2
O
S
O
S
15
16
2
58
CF3
CF3
O
S
O
S
S
3
2
90
90
O
O
O
O
S
S
S
COMe
COMe
17
18
N
N
CF3
S
N
unidentified product mixture
S
a Yield of purified product. All products were characterized by 1H, 13C NMR and HRMS/elemental analysis data.
In conclusion, the ruthenium-catalyzed oxidation pro-
cedure described herein is simple and can be used to oxi-
dize a wide variety of aromatic sulfides to sulfones under
environmentally friendly conditions. A wide variety of
functional groups are tolerated under the reaction condi-
tions. This procedure has the potential to be accepted as a
green chemistry procedure.
Sulfides were purchased from Sigma–Aldrich Chemical Company, In-
dia, or prepared in the laboratory. All other chemicals and solvents
were purchased from Sigma–Aldrich Chemical Company, India.
All products listed in the Table 2 were characterized by IR, NMR (1H,
13C, and DEPT135), mp and HRMS data. IR spectra were recorded on a
Thermo-Nicolet Nexus 670 spectrophotometer. NMR spectra were re-
corded on a Bruker 500 MHz spectrometer. Melting points were de-
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M. H. Ali et al.
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termined using a MeltTemp apparatus. HRMS data were collected on
a QToF Mass Analyzer. Spectral data of known compounds were com-
pared with published data, and references are listed accordingly.
Phenyl-4-methylphenyl Sulfone (Table 2, Entry 4)
Yield of sulfone: 181.5 mg (78%); gummy solid. Yield of sulfoxide:
37 mg (17%).
IR (KBr): 548, 654, 687, 729, 818, 1107, 1157, 1296, 1306, 1319, 1447,
Preparation of the Solid-Supported Reagent
1593, 2986, 2970, 3057 cm–1
.
RuCl3–Al2O3 reagent was prepared by stirring a mixture of RuCl3
(10 mg) and anhydrous γ-alumina (Al2O3; 2 g) in anhydrous acetone
(10 mL), overnight in a round-bottom flask followed by removal of
acetone under vacuum.
1H NMR (500 MHz, CDCl3): δ = 2.39 (s, 3 H), 7.30 (d, J = 7.2 Hz, 2 H),
7.47 (t, J = 7.2 Hz, 2 H), 7.54 (t, J = 7.2 Hz, 1 H), 7.83 (d, J = 7 Hz, 2 H),
7.93 (d, J = 7 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.66 (CH3), 127.62 (C), 127.84 (2 CH),
129.33 (2 CH), 129.91 (2 C), 133.09 (2 CH), 137.15 (C), 138.80 (C),
142.13 (C).
Oxidation of Diphenylsulphide to Diphenyl Sulfone; General Pro-
cedure (Table 2, Entry 2)83
DEPT 135: 21.55 (CH3), 127.51 (CH), 127.72 (CH), 129.21 (CH), 129.92
(CH), 132.98 (CH).
HRMS: m/z [M + Na]+ calcd for C13H12O2S: 255.045572; found:
Basic γ-alumina (2 g) and sodium metaperiodate (3 mmol) were
placed in a small, round-bottom flask. The basic γ-alumina added
above provided support to the metaperiodate. To the well-stirred
mixture, H2O (1 mL) was added followed by Ru–Al2O3 catalyst (20 mg,
0.0005 mmol RuCl3). After 2–3 min, DMC (6 mL) was added followed
by a solution of diphenylsulphide (1 mmol) in DMC (2 mL). The reac-
tion mixture was stirred at r.t. and the progress of the reaction was
monitored by thin-layer chromatography (TLC). When the reaction
was complete (ca. 2 h), the mixture was filtered, the solid was rinsed
with EtOAc (3 × 6 mL), and the combined filtrate was washed with
brine and dried over anhydrous Na2SO4. Evaporation of the organic
solvent gave the crude product, which was purified by column chro-
matography over silica gel (petroleum ether–EtOAc, 75:25) to provide
the corresponding sulfone.
255.0462.
1-(4-Chlorophenylsulfonyl)-3-fluorobenzene (Table 2, Entry 5)
Yield: 222 mg (82%), the remainder was a mixture of unidentified
products; white solid; mp 175–178 °C.
IR (KBr): 573, 631, 675, 691, 708, 758, 787, 827, 885, 1009, 1080,
1148, 1217, 1323, 1393, 1431, 1476, 1576, 1593, 3067, 3094 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.26–7.30 (t, J = 6.5 Hz, 1 H), 7.50–7.55
(m, 3 H), 7.62–7.63 (d, J = 6.5 Hz, 1 H), 7.72 (d, J = 6.5 Hz, 1 H), 7.90 (d,
J = 6.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 115.10 (CH), 120.88 (CH), 123.52 (CH),
129.31 (2 CH), 129.98 (2 CH), 131.44 (CH), 140.41 (C), 143.37 (C),
161.56 (C), 163.57 (C).
Yield: 209.5 mg (96%); white solid; mp 123 °C.
IR (KBr): 3080, 3066, 2781, 2459, 2330, 1969, 1898, 1770, 1579, 1475,
1448, 1309, 1155 cm–1
.
DEPT 135: 115.04 (CH), 120.82 (CH), 123.46 (CH), 129.25 (CH), 129.92
(CH), 131.38 (CH).
1H NMR (500 MHz, CDCl3): δ = 7.50 (t, J = 7.5 Hz, 4 H), 7.56 (t, J = 7 Hz,
2 H), 7.95 (d, J = 7.5 Hz, 4 H).
Anal. Calcd for C12H8ClFO2S: C, 53.24; H, 2.98. Found: C, 52.98; H, 2.64.
13C NMR (125 MHz, CDCl3): δ = 127.80 (4 CH), 129.41 (4 CH), 133.31
(2 CH), 141.76 (2 C).
1-(4-Chlorophenylsulfonyl)-4-nitrobenzene (Table 2, Entry 6)
Yield: 286 mg (96%); yellowish solid; mp 173–174 °C.
DEPT 135: 127.66 (CH), 129.27 (CH), 133.17 (CH).
HRMS: m/z [M + Na]+ calcd for C12H10O2S: 241.029922; found:
241.0288.
IR (KBr): 3107, 3034, 1909, 1605, 1531, 1477, 1402, 1352, 1325, 1157,
1089, 1013, 856, 768, 735 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.52 (d, J = 9 Hz, 2 H), 7.90 (dd, J = 2,
9 Hz, 2 H), 8.11 (dd, J = 2, 9 Hz, 2 H), 8.35 (d, J = 9 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 124.77 (2 CH), 129.13 (2 CH), 129.62
(2 CH), 130.20 (2 CH), 138.70 (CH), 141.20 (CH), 147.11 (CH), 150.65
(CH).
Methylphenyl Sulfone (Table 2, Entry 1)83
Yield: 142 mg (91%); white solid; mp 86 °C.
IR (KBr): 528, 689, 748, 789, 963, 1086, 1148, 1287, 1329, 2896, 2969,
3009 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 3.06 (s, 3 H), 7.48–7.60 (t, J = 7 Hz,
2 H), 7.63–7.70 (t, J = 7 Hz, 1 H), 7.90–7.95 (d, J = 7 Hz, 2 H).
DEPT 135: 124.65 (CH), 129.00 (CH), 129.49 (CH), 130.08 (CH).
Anal. Calcd for C12H8ClNO4S: C, 48.41; H, 2.71; N, 4.70. Found: C,
48.83; H, 2.68; N, 4.74.
13C NMR (125 MHz, CDCl3): δ = 44.63 (CH3), 127.50 (CH), 129.5 (CH),
133.8 (2 C), 140.8 (2 C); DEPT 135: 44.50 (CH3), 127.36 (CH), 129.37
(CH), 133.69 (CH).
1-[4-(4-Chlorophenylsulfonyl)phenyl]ethanone (Table 2, Entry 7)
Yield: 209 mg (71%), the remainder was a mixture of unidentified
products; white solid; mp 128–129 °C.
1-(4-Chlorophenylsulfonyl)-4-cyanobenzene (Table 2, Entry 3)
Yield: 272 mg (98%); gummy solid.
IR (KBr): 3092, 3040, 1697, 1576, 1474, 1396, 1321, 1259, 1153, 1127,
IR (KBr): 552, 590, 640, 704, 754, 798, 837, 849, 1013, 1071, 1090,
1012, 962 cm–1
.
1155, 1289, 1323, 1396, 1478, 1580, 2236, 3042, 3065, 3090 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.62 (s, 3 H), 7.49 (d, J = 8.5 Hz, 2 H),
7.88 (d, J = 8 Hz, 2 H), 8.01 (d, J = 8.5 Hz, 2 H), 8.06 (d, J = 8.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 26.99 (CH3), 128.13 (2 CH), 129.31
(2 CH), 129.46 (2 CH), 129.97 (2 CH), 139.49 (CH), 140.62 (CH),
140.71 (CH), 145.17 (CH), 196.77 (C=O).
1H NMR (500 MHz, CDCl3): δ = 7.55 ( J = 8.6 Hz, 2 H), 7.83 (d, J =
8.6 Hz, 2 H), 7.91 (d, J = 8.4 Hz, 2 H), 8.06 (d, J = 8.6 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 141.09, 138.78, 133.31, 130.14, 129.56
(2 C),128.41 (2 C), 117.34 (2 C), 117.14 (2 C).
HRMS: m/z [M + Na]+ calcd for C13H8NClO2S: 299.986199; found:
DEPT 135: 26.86 (CH3), 128.00 (CH), 129.17 (CH), 129.31 (CH), 129.83
(CH).
299.9862.
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HRMS: m/z [M + Na]+ calcd for C14H11ClO3S: 317.0015; found:
HRMS: m/z [M + Na]+ calcd for C13H12O3S: 271.040487; found:
317.0015.
270.9596.
1-[4-(4-Chlorophenylsulfonyl)phenyl]ethanal (Table 2, Entry 8)
Yield: 267 mg (95%); gummy solid.
1-(4-Chlorophenylsulfonyl)-3,5-dimethylbenzene (Table 2, Entry
12)
Yield: 180 mg (64%), the remainder was a mixture of unidentified
products; white solid; mp 137–139 °C.
IR (KBr): 3078, 3020, 1687, 1672, 1587, 1387, 1285, 1169, 1082, 1011,
820 cm–1
.
IR (KBr): 3084, 2955, 2916, 1908, 1764, 1607, 1578, 1472, 1391, 1321,
1H NMR (500 MHz, CDCl3): δ = 7.25 (d, J = 7 Hz, 2 H), 7.39 (d, J = 7 Hz,
2 H), 7.44 (d, J = 7 Hz, 2 H), 7.74 (d, J = 7 Hz, 2 H), 9.92 (s, 1 H).
13C NMR (125 MHz, CDCl3): δ = 127.72 (2 CH), 130.19 (C), 130.30
(2 CH), 130.38 (2 CH), 134.20 (C), 135.54 (2 CH), 135.61 (C), 146.46
(C),191.24 (COH).
1151, 1084 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.43 (s, 6 H), 7.26 (s, 1 H), 7.54 (d, J =
8 Hz, 2 H), 7.60 (s, 2 H), 7.94 (d, J = 8.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.36 (2 CH3), 125.30 (2 CH), 129.22
(2 CH), 129.68 (2 CH), 135.30 (2 CH), 139.69 (C), 139.83 (C), 140.63
(C), 141.05 (C).
DEPT 135: 127.55 (CH), 130.04 (CH), 130.24 (CH), 135.41 (CH), 191.11
(CHO).
DEPT 135: 21.21 (CH3), 125.15 (CH), 129.07 (CH), 129.54 (CH), 135.16
(CH).
HRMS: m/z [M + Na]+ calcd for C14H13ClO2S: 303.022250; found:
2-(3,5-Dimethylphenylsulfonyl)pyridine (Table 2, Entry 9)
Yield: 240 mg (97%); white solid; mp 97 °C.
303.0221.
IR (KBr): 3053, 2953, 1607, 1574, 1454, 1323, 1271, 1165, 1149, 1120,
987 cm–1
.
Anal. Calcd for C14H13ClO2S: C, 59.89; H 4.67. Found: C, 60.21; H 3.95.
1H NMR (500 MHz, CDCl3): δ = 2.36 (s, 6 H), 7.21 (s, 1 H), 7.40–7.46
(m, 1 H), 7.66 (s, 2 H), 7.90–7.93 (m, 1 H), 8.19 (d, J = 8 Hz, 1 H), 8.68
(br s, 1 H).
2-(2,6-Dimethylphenylsulfonyl)-1,3-dimethoxybenzene (Table 2,
Entry 13)
Yield: 317 mg (89%); white solid; mp 153–155 °C.
13C NMR (125 MHz, CDCl3): δ = 21.33, 122.35, 126.50, 126.93, 135.67,
138.18, 139.05, 139.36, 150.60, 159.40.
HRMS: m/z [M + Na]+ calcd for C13H13NO2S: 270.056471; found:
270.0566.
IR (KBr): 2972, 2941, 2837, 1584, 1474, 1429, 1310, 1254, 1155, 1107,
779 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.59 (s, 6 H), 3.69 (s, 6 H), 6.55 (d, J =
8.5 Hz, 2 H), 7.04 (d, J = 7.5 Hz, 2 H), 7.21 (t, J = 7.5 Hz, 1 H), 7.38 (t, J =
8.5 Hz, 1 H).
Ethyl 4-(4-Bromophenylsulfonyl)ethylbenzoate (Table 2, Entry 10)
13C NMR (125 MHz, CDCl3): δ = 21.69 (2 CH3), 56.40 (2 C), 105.34
(2 C), 130.73 (2 C), 131.33 (2 C), 134.49 (2 C), 139.07 (2 C), 159.43
(2 C).
Yield: 288 mg (78%), the remainder was a mixture of unidentified
products; white solid; mp 125–126 °C.
IR (KBr): 3097, 2980, 1722, 1574, 1400, 1325, 1273, 1155, 1099,
HRMS: m/z [M + Na]+ calcd for C16H18O4S: 329.082352; found:
1009 cm–1
.
329.0824.
1H NMR (500 MHz, CDCl3): δ = 1.39 (t, J = 7.5 Hz, 3 H), 4.37–4.42 (q, J =
7.5 Hz, 2 H), 7.66 (d, J = 7.5 Hz, 2 H), 7.80 (d, J = 7.5 Hz, 2 H), 7.98 (d,
J = 7.5 Hz, 2 H), 8.16 (d, J = 7.5 Hz, 2 H).
1-(4-Chlorophenylsulfonyl)-4-bromobenzene (Table 2, Entry 14)
Yield: 302 mg (91%); white solid; mp 139–140 °C.
IR (KBr): 3092, 1574, 1474, 1393, 1327, 1281, 1159, 1009, 824 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.49 (d, J = 8.5 Hz, 2 H), 7.65 (d, J =
8.5 Hz, 2 H), 7.78 (d, J = 8.5 Hz, 2 H), 7.86 (d, J = 8.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 128.93 (C), 129.27 (2 CH), 129.32
13C NMR (125 MHz, CDCl3): δ = 14.37 (CH3), 61.94 (CH2), 127.81
(2 CH), 129.14 (C), 129.49 (2 CH), 130.68 (2CH), 132.93 (2 CH), 135.08
(C), 140.12 (C), 145.05 (C), 165.04 (C=O).
.
DEPT 135: 14.36 (CH3), 61.80 (CH2), 127.66 (CH), 129.34 (CH), 130.54
(CH), 132.79 (CH).
HRMS: m/z [M + Na]+ calcd for C15H13BrO4S: 390.961563; found:
(2 CH), 129.92 (2 CH), 132.91 (2 CH), 139.87 (C), 140.41 (C), 140.48
(C).
390.9614.
DEPT 135: 129.12 (CH), 129.17 (CH), 129.77 (CH), 132.75 (CH).
HRMS: m/z [M + Na]+ calcd for C12H8BrClO2S: 352.901461; found:
352.8960.
Phenyl-4-methoxyphenyl Sulfone (Table 2, Entry 11)
Yield: 245 mg (97%); gummy solid.
IR (KBr): 558, 687, 731, 804, 835, 1018, 1107, 1152, 1265, 1298, 1317,
1447, 1497, 1576, 1591, 2845, 2945, 2999, 3077 cm–1
.
3-(4-Bromophenylsulfonyl)-1-methyl-4-nitrobenzene (Table 2,
1H NMR (500 MHz, CDCl3): δ = 3.85 (s, 3 H), 6.96–6.99 (d, J = 8.5 Hz,
2 H), 7.48–7.55 (m, 3 H), 7.88 (d, J = 8.5 Hz, 2 H), 7.93 (d, J = 8.5 Hz,
2 H).
Entry 15)
Yield: 206.5 mg (58%), the remainder was a mixture of unidentified
products; white solid; mp 190–192 °C.
13C NMR (125 MHz, CDCl3): δ = 55.78 (CH3), 114.66 (2 CH), 127.46
(2 CH), 129.34 (2 CH), 130.04 (2 CH), 132.96 (2 CH), 133.31 (C),
142.55 (C), 163.54 (C).
IR (KBr): 3091, 2951, 2879, 1933, 1568, 1535, 1475, 1389, 1358, 1313,
1153, 1066, 887 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.56 (s, 3 H), 7.54 (d, J = 7 Hz, 1 H),
7.68–7.71 (m, 3 H), 7.83 (d, J = 7.5 Hz, 2 H), 8.17 (s, 1 H).
DEPT 135: 55.63 (CH3), 114.51 (CH), 127.32 (CH), 129.19 (CH), 129.89
(CH), 132.83 (CH).
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13C NMR (125 MHz, CDCl3): δ = 21.69 (CH3), 123.46 (C), 125.37 (CH),
127.10 (C), 129.17 (C), 129.89 (CH), 132.14 (CH), 132.51 (CH), 134.37
(C), 135.15 (CH), 139.87 (C), 144.53 (C).
(5) Carlson, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org.
Chem. 1981, 46, 3936.
(6) Gore, E. S. Platinum Met. Rev. 1983, 27, 111.
(7) Yamaoka, H.; Moriya, N.; Ikunaka, M. Org. Process Res. Dev.
2004, 8, 931.
(8) Desai, S. M.; Halligudi, N. N.; Nandibewoor, S. T. Transition Met.
Chem. (Dordrecht, Neth.) 2002, 27, 207.
(9) Giddings, S.; Mills, A. J. Org. Chem. 1988, 53, 1103.
(10) Plietker, B.; Niggemann, M. Org. Biomol. Chem. 2004, 2, 2403.
(11) Plietker, B. J. Org. Chem. 2004, 69, 8287.
(12) Spitzer, U. A.; Lee, D. G. J. Org. Chem. 1975, 40, 2539.
(13) Wolfe, S.; Hasan, S. K.; Campbell, J. R. Chem. Commun. 1970,
1420.
(14) Rangaswami, M.; Anand, S.; Gowda, N. M. M. Synth. React. Inorg.
Met.-Org. Chem. 2001, 31, 1479.
(15) Yusubov, M. S.; Chi, K.-W.; Park, J. Y.; Karimov, R.; Zhdankin, V.
V. Tetrahedron Lett. 2006, 47, 6305.
(16) Barak, G.; Dakka, A.; Sasson, Y. J. Org. Chem. 1988, 53, 3553.
(17) Shingate, B. B.; Hazra, B. G.; Salunke, D. B.; Pore, V. S. Tetrahe-
dron Lett. 2011, 52, 6007.
DEPT 135: 21.54 (CH3), 125.23 (CH), 129.74 (CH), 132.00 (CH), 132.36
(CH), 135.01 (CH).
HRMS: m/z [M + H]+ calcd for C13H10BrNO4S: 355.9592; found:
355.9492.
1-(4-Tosylphenoxy)-3-(trifluoromethyl)benzene (Table 2, Entry
16)
Yield: 353 mg (90%); yellow viscous liquid.
IR (neat): 3099, 3057, 1857, 1679, 1578, 1518, 1429, 1362, 1323,
1261, 1167, 1119, 1018 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.37 (s, 3 H), 7.04 (d, J = 7 Hz, 2 H), 7.21
(d, J = 8 Hz, 1 H), 7.30 (m, 3 H), 7.45 (d, J = 7.5 Hz, 1 H), 7.51 (t, J = 8 Hz,
1 H), 7.83 (d, J = 8 Hz, 2 H), 7.92 (d, J = 8 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 21.6 (CH3), 60.45 (CF3), 117.10 (CH),
117.13 (2 CH), 118.34 (CH), 121.57 (CH), 123.36 (CH), 127.67 (2 CH),
130.07 (2 CH), 130.16 (C), 130.92 (2 CH), 136.75 (C), 138.94 (C),
144.27 (C), 155.64 (C), 16.91 (C).
(18) Murahashi, S.-I.; Naota, T.; Miyaguchi, N.; Noda, S. J. Am. Chem.
Soc. 1996, 118, 2509.
HRMS: m/z [M
393.0766.
+
H]+ calcd for C20H15F3O3S: 393.0772; found:
(19) Cheung, W.-H.; Yip, W.-P.; Yu, W.-Y.; Che, C.-M. Can. J. Chem.
2005, 83, 521.
(20) Murahashi, S.-I.; Saito, T.; Hanaoka, H.; Murakami, Y.; Naota, T.;
Kumobayashi, H.; Akutagawa, S. J. Org. Chem. 1993, 58, 2929.
(21) Komiya, N.; Noji, S.; Murahasi, S.-I. Chem. Commun. 2001, 65.
(22) Jain, S. L.; Sain, B. Chem. Commun. 2002, 1040.
(23) Ragagnin, G.; Knochel, P. Synlett 2004, 951.
(24) Shiroishi, H.; Nukaga, M.; Yamashita, S.; Kaneko, M. Chem. Lett.
2002, 488.
(25) Chang, S.; Lee, M.; Ko, S.; Lee, P. Synth. Commun. 2002, 32, 1279.
(26) Matsumoto, M.; Watanabe, N. J. Org. Chem. 1984, 49, 3435.
(27) Jain, S. L.; Sharma, V. B.; Sain, B. Synth. Commun. 2005, 35, 465.
(28) Sharma, V. B.; Jain, S. L.; Sain, B. Tetrahedron Lett. 2004, 45,
4281.
(29) Yang, D.; Zhang, C. J. Org. Chem. 2001, 66, 4815.
(30) Plietker, B. J. Org. Chem. 2003, 68, 7123.
(31) Gross, Z.; Ini, S. Org. Lett. 1999, 1, 2077.
(32) Zhang, R.; Yu, W.-Y.; Wong, K.-Y.; Che, C.-M. J. Org. Chem. 2001,
66, 8145.
1-[5-(Pyridin-3-ylsulfonyl)thiophen-2-yl]ethanone (Table 2, Entry
17)
Yield: 244 mg (90%); white solid; mp 149–150 °C.
IR (KBr): 2998, 1975, 1684, 1601, 1568, 1422, 1357, 1258, 1178 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 2.57 (s, 3 H), 7.50–7.54 (m, 1 H), 7.62
(d, J = 7.5 Hz, 1 H), 7.83 (d, J = 7.5 Hz, 1 H), 7.94–7.98 (m, 1 H), 8.20 (d,
J = 8 Hz, 1 H), 8.71–8.2 (br d, 1 H).
13C NMR (125 MHz, CDCl3): δ = 27.11 (CH3), 122.20 (CH), 127.59 (CH),
131.42 (CH), 135.13 (CH), 138.51 (CH), 146.16 (C), 150.75 (CH),
151.60 (C), 158.19 (C), 190.41 (C=O).
DEPT 135: 26.99 (CH3), 122.07 (CH), 127.47 (CH), 131.13 (CH), 135.01
(CH), 138.38 (CH), 150.63 (CH).
HRMS: m/z [M
+
H]+ calcd for C11H9NO3S2: 268.0102; found:
268.0098.
(33) Nunez, M. T.; Martin, V. S. J. Org. Chem. 1990, 55, 1928.
(34) Shoair, A. G.; Mohamed, R. H. Synth. Commun. 2006, 36, 59.
(35) Kraft, P.; Eichenberger, W. Eur. J. Org. Chem. 2003, 3735.
(36) Webster, F. X.; Rivas-Enterrios, J.; Silverstein, R. M. J. Org. Chem.
1987, 52, 689.
Acknowledgment
The authors are grateful for the financial support from the National
Science Foundation (NSF)-IRES grant number OISE-0966395.
(37) Mazoir, N.; Auhmani, A.; Daubi, M. Synth. Commun. 2007, 37,
1289.
(38) Akbutina, F. A.; Torosyan, S. A.; Vostrikov, N. S.; Spririkhin, L. V.;
Miftakhov, M. S. Russ. Chem. Bull. 1996, 45, 2813.
(39) Ziyat, H.; Ali, M. A.; Karim, A.; Meliet, C.; Castanet, Y.; Mortreux,
A. Acta Chim. Slov. 2004, 51, 223.
(40) Parikh, V. M.; Jones, J. K. N. Can. J. Chem. 1965, 43, 3452.
(41) Phukan, P.; Sudalai, A. J. Chem. Soc., Perkin Trans. 1 1999, 3015.
(42) Hjelmencrantz, A.; Berg, U. J. Org. Chem. 2002, 67, 3585.
(43) Han, J.-S.; Lowary, T. L. J. Org. Chem. 2003, 68, 3735.
(44) Sarker, T. K.; Basak, S. Org. Lett. 2004, 6, 2925.
(45) Ferraz, H. M.; Longo, L. S. Org. Lett. 2003, 5, 1337.
(46) Alcaide, B.; Almendros, P.; Alonso, J. M. Tetrahedron Lett. 2003,
44, 8693.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1560834.
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ortiInfogrmoaitn
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p
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References
(1) Djerrasi, C.; Engle, R. R. J. Am. Chem. Soc. 1953, I75, 3838.
(2) Naota, T.; Takaya, H.; Murahasi, S.-I. Chem. Rev. 1998, 98, 2599.
(3) Plietker, B. Synthesis 2005, 2453.
(4) Pagliaro, M.; Campestrini, S.; Ciriminna, R. Chem. Soc. Rev. 2005,
34, 837.
(47) Torii, S.; Inokuchi, T.; Kondo, K. J. Org. Chem. 1985, 50, 4980.
(48) Yuasa, Y.; Tsuruta, H. J. Essent. Oil Res. 1998, 10, 39.
(49) Morris, P. E.; Kiely, D. E. J. Org. Chem. 1987, 52, 1149.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 429–436

436
M. H. Ali et al.
Paper
Synthesis
(50) Yuasa, Y.; Shibuya, S.; Yuasa, Y. Synth. Commun. 2003, 33, 3947.
(51) Rup, S.; Sindt, M.; Oget, N. Tetrahedron Lett. 2010, 51, 3123.
(52) Plietker, B.; Niggemann, M. J. Org. Chem. 2005, 70, 2402.
(53) Ali, M. H.; Niedbalsky, M.; Bohnert, G.; Bryant, D. Synth.
Commun. 2006, 36, 1751.
(69) Gallagher, L. A.; Meyer, T. J. J. Am. Chem. Soc. 2001, 123, 5308.
(70) Arini, G. A.; Szeto, P.; Hughes, D. L.; Stockman, R. A. Tetrahedron
Lett. 2004, 45, 8371.
(71) Kimberley, M. ChemSpider SyntheticPage 2002, 186; DOI:
10.1039/SP186.
(54) Ali, M. H.; Wiggin, C. J. Synth. Commun. 2001, 3383.
(55) Ali, M. H.; Wiggin, C. J. Synth. Commun. 2001, 1389.
(56) Ali, M. H.; Leach, D. R.; Schmitz, C. E. Synth. Commun. 1998,
2969.
(57) Ali, M. H.; Bohnert, G. J. Synth. Commun. 1998, 2983.
(58) Ali, M. H.; Bohnert, G. J. Synthesis 1997, 764.
(59) Cheung, W.-H.; Yu, W.-Y.; Yip, W.-P.; Zhu, N.-Y.; Che, C.-M.
J. Org. Chem. 2002, 67, 7716.
(72) Rinner, U.; Siengalewicz, P.; Hudlicky, T. Org. Lett. 2002, 4, 115.
(73) Sharma, N. K.; Ganesh, K. N. Tetrahedron Lett. 2004, 45, 1403.
(74) Plietker, B.; Niggemann, M. Org. Lett. 2003, 5, 3353.
(75) Griffith, P.; Kwong, E. Synth. Commun. 2003, 33, 2945.
(76) Paquette, L. A.; Kahane, A. L.; Seekamp, C. K. J. Org. Chem. 2004,
69, 5555.
(77) Zimmermann, F.; Meux, E.; Mieloszynski, J.-L.; Lecuire, J.-M.;
Oget, N. Tetrahedron Lett. 2005, 46, 3201.
(60) Tchener, Y. N.; Choukchou-Braham, A.; Bachir, R. Bull. Mater. Sci.
2012, 35, 673.
(78) Moutevelis-Minakakis, P.; Sinanoglou, C.; Loukas, V.; Kokotos,
G. Synthesis 2005, 933.
(61) Amama, P. B.; Itoh, K.; Murabayashi, M. J. Mater. Sci. 2004, 39,
4349.
(79) Yang, D.; Chen, F.; Dong, Z.-M.; Zhang, D.-W. J. Org. Chem. 2004,
69, 2221.
(62) Zhan, B.-Z.; White, M. A.; Pincock, J. A.; Robertson, K. N.;
Cameron, T. S.; Sham, T.-K. Can. J. Chem. 2003, 764.
(63) Zhan, B.-Z.; White, M. A.; Sham, T.-K.; Pincock, J. A.; Doucet, R. J.;
Rao, K. V. R.; Robertson, K. N.; Cameron, T. S. J. Am. Chem. Soc.
2003, 125, 2195.
(64) Yamaguchi, K.; Mizuno, N. Angew. Chem. Int. Ed. 2002, 41, 4538.
(65) Yamaguchi, K.; Mizuno, N. Angew. Chem. Int. Ed. 2003, 42, 1480.
(66) Ho, C.-M.; Yu, W.-Y.; Che, C.-M. Angew. Chem. Int. Ed. 2004, 43,
3303.
(80) Cornely, J.; Ham, L. M. S.; Meade, D. E.; Dragojlovic, V. Green
Chem. 2003, 5, 34.
(81) Tundo, P.; Avico, F.; Anthony, E. R.; Grego-Rossi, S. Dimethyl Car-
bonate: Green Solvent and Ambient Reagent, In Green Chemical
Reactions, NATO Science for Peace and Security Series; Tundo, P.;
Esposito, V., Eds.; Springer: Dordrecht, 2008, 213–232.
(82) Yu, B.; Liu, A.-H.; He, L.-N.; Li, B.; Diazo, Z.-F.; Li, Y.-N. Green
Chem. 2012, 14, 957.
(83) Kim, S. S.; Nehru, K.; Kim, S. S.; Kim, D. W.; Jung, H. C. Synthesis
2002, 2484.
(67) Yamaguchi, K.; Mizuno, N. Angew. Chem. 2003, 115, 1518.
(68) Qian, G.; Zhao, R.; Lu, G.; Qi, Y.; Suo, J. Synth. Commun. 2004, 34,
1753.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 429–436