α-diketone formation accompanied by oxidation of sulfur functional group by the reaction of o-alkynylarenesulfoxide with iodine

Article abstract of DOI:10.1021/jo3023186

The reaction of o-alkynylarenesulfoxide with iodine was investigated in detail, revealing functionalities of the formation of α-diketones with sulfenyl, sulfinyl, and sulfonyl. Additives can change the ratio of products to give medium-to-excellent yields.

Full text of DOI:10.1021/jo3023186

Note
pubs.acs.org/joc
α‑Diketone Formation Accompanied by Oxidation of Sulfur
Functional Group by the Reaction of o‑Alkynylarenesulfoxide with
Iodine
Shoji Matsumoto,* Hiroyuki Shibata, and Motohiro Akazome
Department of Applied Chemistry, Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoicho, Inageku, Chiba
263-8522, Japan
S
* Supporting Information
ABSTRACT: The reaction of o-alkynylarenesulfoxide with iodine was
investigated in detail, revealing functionalities of the formation of α-
diketones with sulfenyl, sulfinyl, and sulfonyl. Additives can change the ratio
of products to give medium-to-excellent yields. Results show that water is
taken into only sulfonyl compound and that other oxygen atoms
constructed in the products are presumably derived from sulfoxide of the
starting material and molecular oxygen.
a
Table 1. α-Diketone Formation by the Reaction of 1 with I2
rganic synthesis without transition metals is examined
Ointensively by academic scientists and manufacturers
because of resource problems. Iodine is an easily handled
halogen molecule in organic synthesis because of its stability
and easy handling as a solid under ambient conditions.1 In
various organic reactions using I2, investigations have been
made of the electrophilic activation of alkynes with I2 to
produce iodinated compounds2 such as heteroaromatics,3−6
fused aromatics,7 benzenes,8 and cyclic vinyl iodides,8a,9 which
are important for the construction of novel functional materials.
Therefore, the activation of alkynes with I2 presents the
potential for use with organic synthesis. Actually, some reports
describe the reaction of alkynes with I2 in DMSO to give α-
diketones.10,11 Sakthivel and Srinivasan recently reported the
formation of α-diketones by the reaction of o-alkynylarene-
carboxaldehydes with I2/H2O.12 A similar reaction using o-
alkynylarenesulfoxide was also reported by Chen and co-
workers.13 They obtained α-diketones bearing sulfenyl group in
moderate to good yield. The net reaction involves the oxidation
of alkynyl part with the reduction of the sulfoxide moiety. We
examined the reaction reported by Chen et al. just in time for
publication. However, we obtained additional unprecedented
information related to this reaction to give the compounds
having the different oxidation state of sulfur. We herein report
results of our detailed investigation of the reaction of o-
alkynylarenesulfoxide with I2. We found a unique additive effect
to give the corresponding α-diketones.
yield (%)
entry
additives (equiv)
NaHCO3 (2.0)
2
3
4
b
1
68
2
45
19
31
9
5
9
c
3
53
d
4
14
trace
4
e
5
f
8
21
3
6
trace
6
g
7
8
NIS (1.0)
39
11
11
h
NBS (1.0)
no reaction
i
9
35
52
35
21
10
51
97
51
33
13
50
15
32
0
10
15
5
j
10
k
11
12
O2
H2O (3.0)
13
42
11
0
l
13
K2CO3 (1.8)
14
15
Phenol (1.2)
Phenol (1.2) + K2CO3 (1.0)
a
b
Reaction conditions: 1 molar equiv of I2 in CHCl3 for 1 d. Reference
4. Conditions: 2 molar equiv of I2 in CH2Cl2 for 8 h. In CH3CN. In
THF. In toluene. In MeOH. NIS was used instead of I2. Reacted for
2 d. NBS was used instead of I2. 2 molar equiv of I2 was used. Under
c
d
e
f
g
Chen and co-workers reported a reaction of 1-(methyl-
sulfinyl)-2-(2-phenylethynyl)benzene (1) with I2 in CH2Cl2 in
the presence of NaHCO3 to give α-diketone with a
methylsulfenyl group (2) in 68% yield (Table 1, entry 1).
When we examined this reaction in CHCl3 without NaHCO3,
the formation of 2 accompanied by 3 and 4 was observed,
although the main product was 2 (entry 2). When various
solvents were examined, the formation of three compounds was
observed in varying ratios (entries 3−6). The reaction was
h
i
j
k
l
air atmosphere. O2 atmosphere. 1 was recovered in 28% yield.
inhibited in MeOH because of complexation of alcohol with I2
(entry 6). This reaction proceeded using N-iodosuccinimide
Received: October 22, 2012
Published: January 22, 2013
© 2013 American Chemical Society
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Note
Figure 1. Results of EI-Mass spectrographs obtained from the reaction (a) without and (b) with H218O. (c) Obtained fragment patterns of 4.
(NIS) as the I+ source, although the reaction with NBS did not
occur (entries 7 and 8). Therefore, the I+ source is necessary to
achieve the α-diketone formation. Surprisingly, when the
amount of I2 was changed, 3 was obtained as a main product
in 51% yield (entry 9).
with a small intensity of the original peak ([M − COC6H5]+ =
183) (Figure 1b). However, the peak from the loss of SO2Me
moiety was mainly observed in the same value ([M − SO2Me]+
= 209). These results suggest that the oxygen of H2O is
introduced to sulfonyl moiety in 4.
Furthermore, we examined the additives to improve the yield
of each product in addition to giving information about the
reaction mechanism. When the reaction was conducted under
air atmosphere, the yields of 2−4 were slightly increased (entry
10). On the contrary, under O2 atmosphere, the yields of α-
diketones were decreased with the formation of side products
which were not obtained in the standard conditions (entry 2 vs
10). By addition of H2O, the formation of 3 was observed in
50% yield (entry 12). The addition of K2CO3 was efficient to
increase 4 as a main product (entry 13). Excellent yield of 2 was
obtained in the presence of both phenol and K2CO3 (entry 15),
whereas a slight increase of the yield of 2 was observed (entry
14).
In these reactions, we noticed two problems: (1) source of
oxygen on diketone and sulfur oxide and (2) reaction
mechanisms for 2−4. We first investigated the oxygen source
using H218O. The reaction with 3 equiv of H218O was
conducted in anhydrous CHCl3 with molecular sieves 4A
before use. According to the mechanism proposed by Chen,
18O enriched 2 should be obtained because one of two oxygens
in diketone is derived from H2O. However, from mass
spectroscopic analysis of the obtained compounds, the 18O
enrichment was observed only in 4, and 18O enrichments of 2
and 3 were within the margin of error.14 Therefore, H2O is
directly related only to the formation of 4. Furthermore, the
investigation of the fragmentation from 4 helps to infer the
position of 18O enriched oxygen. When 4 derived from the
reaction without H218O was examined using EI-Mass spectros-
copy, the fragmentation peaks were observed along with the
parent peak ([M]+ = 288). The analysis revealed that the
removal of each of the SO2Me part and COC6H5 part occurred
to give [M − SO2Me]+ = 209 and [M − COC6H5]+ = 183
peaks, respectively (Figure 1a). The large value by two mass
was obtained in the parent peak ([M + 2]+ = 290) of 4 derived
from the reaction within H218O (Figure 1b). Furthermore, the
fragment peak derived from the loss of COC6H5 moiety gave
the large value ([M + 2-COC6H5]+ = 185) as the main peak
In some reactions, the yields of 2 and 3 were higher than
50% under N2 or Ar atmosphere (Table 1, entries 3, 9, 12, 14,
and 15), which implies exclusion of the possibility of the
oxygen at sulfoxide of 1 as both oxygen sources of diketones.
Furthermore, from investigation of the reaction in CDCl3 with
NMR analysis, the products of 2−4 were recognizable without
workup (see Figure S1, Supporting Information). Therefore, we
suspected molecular oxygen as another oxygen source. We
conducted the reaction in a vessel equipped with N2 or Ar
balloon made from latex. However, we were unable to neglect
the exchange of gases in the balloon in a period of the reaction
time (1−2 d). Therefore, the reaction was examined under
sealed conditions. After the addition of I2 under Ar atmosphere,
the reaction vessel was closed with a glass stopcock. Then the
reaction mixture was stirred at room temperature for 10 h. After
the usual workup, the decrease of the reaction rate was
observed to give 15% recovery of the starting material (1)
against the standard conditions (8%) with decreasing of the
total yield of α-diketones (from 92% to 65%) (Scheme 1).15,16
Therefore, we concluded that the contaminated molecular
oxygen is the oxygen source of some oxygen atoms in the
products.
Next, we tried to solve the reaction mechanism to give each
product. Focusing on the structural differences of the products,
the three products are only different in terms of the oxidation
state on the sulfur atom. However, no oxidation and
disproportionation reactions were observed in between 2−4
(see Scheme S1, Supporting Information). Based on these
results, we proposed the reaction mechanism depicted in
Scheme 2. The activation of alkyne with I2 occurred to form the
corresponding iodovinyl intermediate (A and A′), which is
replicated from Chen’s proposal.13 From the result of the
nonparticipation of H2O at diketone moiety, the ring-opening
reaction proceeds by the addition of molecular oxygen to give
intermediate B, derived from intermediate A.17 When the
reaction is conducted without the additives, intramolecular
electron transfer from iodide to sulfide cation radical occurs to
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Note
radical. Furthermore, the additional acceptance of one electron
from phenol existing in equilibrium with phenoxide under
reaction conditions produces potassium hydroperoxide,18
which is known as a good nucleophile.19 Therefore, the
nucleophilic attack of hydroperoxide anion to the intermediate
A and A′ proceeds to the ring-opening reaction with
subsequent cleavage of C−I and O−O bond with the attack
of iodide to give 2.17
Scheme 1. Effect of Molecular Oxygen with the Reaction
under “Sealed Conditions”
In summary, results show that the α-diketone formation
accompanied oxidation of sulfur atom in the reaction of o-
alkynylarenesulfoxide with I2. Introducing the additives and
ratio of the products can vary in medium-to-excellent yields.
Oxygen sources of the products were also examined, revealing
that both H2O and molecular oxygen are plausible. Based on
those results, we advanced the improved reaction mechanism
based on Chen’s report, which suggests that it is feasible in
organic synthesis to use the complexed reaction starting by the
activation of acetylene with I2. α-Diketones play an important
role in organic synthesis because of their ready conversion into
various materials.20 Consequently, α-diketone formation with
additional functional group transformation can widen the
possibilities for organic synthesis.
give the peroxy radical (path a). After cleavage of O−O bond, 2
is formed. In the case of the addition of H2O (Table 1, entry
12), the polarity of the solvent will be increased to separate
iodide and sulfide cation radical in B. Therefore, the electron
transfer will be difficult, and the radical coupling of B occurs to
give the cyclized intermediate C (path b). When the large
amount of I2 is introduced (Table 1, entry 9), the electron
−
transfer also ceases by the formation of I3 ion by the
EXPERIMENTAL SECTION
General Information. Melting points were uncorrected. NMR
complexation of iodide and I2. The attack of iodide and the O−
O bond cleavage occurred to form 3. These mechanisms are
reliable in the point of solvent effect. By increasing the polarity
of the solvent, increase in the ratio of 3 (and 4) was observed
(Table 1, entries 2 and 3). Furthermore, solutions of THF and
toluene, which can act as radical traps, show low yields of the
products (Table 1, entries 4 and 5). As described above, the
oxygen source of sulfone group is H2O. Furthermore, the
strong basic conditions with K2CO3 promote the formation of
4 (Table 1, entry 13). Therefore, nucleophilic HO− will be
formed from the reaction of H2O and K2CO3. The attack to
positive charge on sulfur atom in intermediate C leads to 4 with
subsequent deprotonation (path c).
The mechanism summarized in Scheme 2 could not explain
the selective formation of 2 in the presence of the combination
of phenol and K2CO3 (Table 1, entry 15). Therefore, another
reaction mechanism can also be applied to the formation of 2.
Considering the antioxidant effect of phenol, the reaction
mechanism depicted in Scheme 3 can be reliable. Molecular
oxygen receives one electron from phenoxide to give anion
■
1
measurements were recorded with a 300 MHz spectrometer for H
NMR and with a 75 MHz spectrometer for 13C NMR. Chemical shifts
1
(δ) of H NMR were expressed in parts per million downfield from
tetramethylsilane in CDCl3 (δ = 0) as an internal standard.
Multiplicities are indicated as s (singlet), bs (broadened singlet), d
(doublet), t (triplet), m (multiplet), and coupling constants (J) are
reported in hertz units. Chemical shifts (δ) of 13C NMR are expressed
in parts per million downfield or upfield from CDCl3 (δ = 77.0) as an
internal standard. Infrared spectra (IR) were recorded on a KBr disk or
on a NaCl plate. Mass spectra were recorded with ESI-Orbitrap
(cation mode) spectrometer. Analytical thin-layer chromatography
(TLC) was performed on glass plates that had been precoated with
silica gel (0.25 mm layer thickness). Column chromatography was
performed on 70−230 mesh silica gel.
Preparation of 1-(Methylsulfinyl)-2-(phenylethynyl)benzene
(1). A mixture of 2-iodothioanisole (0.600 g, 2.40 mmol),
PdCl2(PPh3)2 (25.2 mg, 0.0360 mmol), and CuI (42.0 mg, 0.22
mmol) was dissolved in NEt3 (10 mL). To the solution was added
ethynylbenzene (0.244 g, 2.39 mmol), and the mixture was stirred at
60 °C for 22 h. To the reaction mixture was added H2O (10 mL), with
Scheme 2. Plausible Reaction Mechanism for the Formation of 2−4
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Note
Scheme 3. Another Reaction Mechanism Forming 2 in the Presence of Phenol and K2CO3
subsequent extractraction with CHCl3 (10 mL × 4). The organic layer
was filtered with a pad of Celite, and the filtrate was dried with MgSO4.
After the filtration and evaporation, the yellow solid was obtained as 1-
(methylthio)-2-(phenylethynyl)benzene5a in quantitative yield. The
obtained solid was dissolved in EtOH (100 mL) and H2O (100 mL),
and the solution was added NaIO4 (1.027 g, 4.8 mmol). After being
stirred at room temperature for 5 d, the reaction mixture was extracted
with CHCl3 (10 mL × 4). The organic layer was washed with
saturated aq Na2SO3 (15 mL × 4) and brine (15 mL × 2). After drying
with MgSO4 and evaporation, the residue was subjected to column
chromatography on SiO2 (CHCl3) to give 1-(methylsulfinyl)-2-
(phenylethynyl)benzene (1) (0.286 g, 1.19 mmol, 50%) as a pale
Hz, 1H), 8.17 (d, J = 7.1 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ
44.7, 128.5, 129.1, 131.0, 131.1, 132.2, 132.6, 134.0, 134.3, 137.3,
139.3, 189.0, 192.0; IR (KBr) 3026, 2928, 1679, 1597, 1453, 1411,
1311, 1200, 1185, 1154, 1121, 962, 854, 781, 756, 739, 705, 635, 543,
534 cm−1; HRMS (ESI) calcd for C15H12O4NaS ([M + Na]+)
311.0349, found 311.0338.
Reaction of 1-(Methylsulfinyl)-2-(phenylethynyl)benzene (1)
with I2 and H2O. To a solution of 1 (34.1 mg, 0.142 mmol) in CHCl3
(10 mL) were added H2O (7.8 mg, 0.43 mmol) and I2 (36.1 mg, 0.142
mmol) at room temperature under N2 atmosphere. After the solution
was stirred at room temperature for 1 d, the usual workup was used to
give 2 (7.5 mg, 0.029 mmol, 21%), 3 (19.2 mg, 0.0705 mmol, 50%),
and 4 (5.3 mg, 0.018 mmol, 13%), respectively.
Reaction of 1 with I2 and K2CO3. To a solution of 1 (27.0 mg,
0.112 mmol) in CHCl3 (10 mL) were added K2CO3 (27.2 mg, 0.197
mmol) and I2 (25.5 mg, 0.100 mmol) at room temperature under N2
atmosphere. After the mixture was stirred at room temperature for 1 d,
the usual workup was used to give 2 (2.6 mg, 0.010 mmol, 10%), 3
(4.7 mg, 0.017 mmol, 15%), 4 (13.5 mg, 0.468 mmol, 42%), and
recovered 1 (7.5 mg, 0.031 mmol, 28% recovery), respectively.
Reaction of 1 with I2, Phenol, and K2CO3. To a solution of 1
(60.1 mg, 0.250 mmol) in CHCl3 (2.5 mL) were added I2 (69.5 mg,
0.274 mmol), K2CO3 (32.1 mg, 0.232 mmol), and phenol (29.5 mg,
0.313 mmol) at room temperature under N2 atmosphere. After the
mixture was stirred at room temperature for 1 d, the usual workup was
used to give 2 (62.4 mg, 0.243 mmol, 97%).
1
yellow oil: H NMR (300 MHz, CDCl3) δ 2.88 (s, 3H), 7.38−7.40
(m, 3H), 7.44−7.62 (m, 5H), 7.99 (d, J = 7.8 Hz, 1H); 13C NMR (75
MHz, CDCl3) δ 42.1, 84.2, 98.0, 119.3, 122.0, 123.3, 128.5, 129.2,
129.5, 130.3, 131.5, 132.4, 147.3; IR (NaCl) 3475, 3056, 2216, 1598,
1492, 1463, 1442, 1290, 1124, 1072, 1040, 952, 847, 758, 690 cm−1;
HRMS (ESI) calcd for C15H12ONaS ([M + Na]+) 263.0501, found
263.0499.
Typical Procedure for the Reaction of 1 with I2. To a solution
of 1 (93.1 mg, 0.387 mmol) in CHCl3 (10 mL) was added I2 (98.4 mg,
0.388 mmol) at room temperature under N2 atmosphere. After being
stirred at room temperature for 1 d, to the resultant mixture was added
saturated aq Na2S2O3 (10 mL), with subsequent extraction with
CHCl3 (10 mL × 4). The combined organic layer was dried with
MgSO4. After filtration and evaporation, the residue was subjected to
column chromatography on SiO2 (CHCl3/ EtOAc = 2:1) to give 1-(2-
(methylthio)phenyl)-2-phenylethane-1,2-dione (2) (44.3 mg, 0.173
mmol, 45%), 1-(2-(methylsulfinyl)phenyl)-2-phenylethane-1,2-dione
(3) (20.4 mg, 0.0750 mmol, 19%), and 1-(2-(methylsulfonyl)phenyl)-
2-phenylethan-1,2-dione (4) (5.8 mg, 0.020 mmol, 5%), respectively.
1-(2-(Methylthio)phenyl)-2-phenylethane-1,2-dione (2):11
Reaction under “Sealed Conditions”. Compound 1 (36.0 mg,
0.150 mmol) in a two-neck flask equipped with a two-way stopcock
and rubber septum was dissolved in CHCl3 (5 mL). Dissolved oxygen
was driven out of the solution by bubbling Ar gas for 1 h, followed by
three freeze−thaw cycles. To the solution was added I2 (38.1 mg,
0.150 mmol) in a stream of Ar gas. After addition of I2, the septum was
exchanged for a glass stopcock, and the reaction was conducted under
sealed conditions. After the solution was stirred at room temperature
for 10 h, the usual workup (wash with aq Na2S2O3, extraction with
CHCl3, and dry with MgSO4) gave 49.5 mg of the crude products. The
product ratio was determined by the integration of methyl protons of
1
yellow oil; H NMR (300 MHz, CDCl3) δ 2.46 (s, 3H), 7.23 (t, J =
7.3 Hz, 1H), 7.45 (d, J = 8.1 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 7.57 (t,
J = 8.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.74 (d, J = 7.7 Hz, 1H), 7.99
(d, J = 7.5 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 16.7, 124.6, 127.0,
128.9, 130.0, 131.6, 133.3, 133.4, 133.9, 134.4, 143.5, 193.0, 194.9; IR
(NaCl) 3063, 2923, 2855, 1652, 1587, 1558, 1459, 1451, 1434, 1363,
1320, 1281, 1264, 1208, 1181, 1142, 1081, 1047, 1021, 998, 965, 879,
858, 800, 748, 721, 686, 662, 646 cm−1. HRMS (ESI) calcd for
C15H12O2NaS ([M + Na]+) 279.0450, found 279.0450.
1
1−4 in H NMR analysis with adamantine as an internal standard.
ASSOCIATED CONTENT
■
S
* Supporting Information
1
1-(2-(Methylsulfinyl)phenyl)-2-phenylethane-1,2-dione (3):
NMR spectra for 1−4, H NMR analysis in the reaction of 1
1
pale yellow solid; mp 65.5−67.0 °C; H NMR (300 MHz, CDCl3)
with I2 (Figure S1), oxidation and disproportionation experi-
ments of 2−4 (Scheme S1), and the plausible reaction
mechanisms through intermediate A′ (Schemes S2 and S3).
This material is available free of charge via the Internet at
http://pubs.acs.org.
δ 2.94 (s, 3H), 7.54 (t, J = 7.5 Hz, 2H), 7.60 (dt, J = 1.1 and 7.6 Hz,
1H), 7.70 (t, J = 7.4 Hz, 1H), 7.87 (d, J = 7.8 Hz, 1H), 7.93 (dd, J =
1.1 and 7.2 Hz, 1H), 7.94 (d, J = 7.9 Hz, 2H), 8.47 (d, J = 7.2 Hz, 1H);
13C NMR (75 MHz, CDCl3) δ 43.7, 125.0, 129.1, 129.5, 129.9, 130.4,
132.4, 133.1, 135.3, 135.6, 151.3, 192.7, 194.6; IR (NaCl) 3461, 2990,
2924, 1668, 1595, 1569, 1451, 1436, 1421, 1324, 12127, 1177, 1165,
1137, 1074, 1049, 1030, 998, 968, 957, 945, 893, 870, 793, 750, 719,
693, 685, 663, 645, 615 cm−1; HRMS (ESI) calcd for C15H12O3NaS
([M + Na]+) 295.0399, found 295.0398.
AUTHOR INFORMATION
Corresponding Author
*Tel: +81-43-290-3369. Fax: +81-43-290-3401. E-mail address:
smatsumo@faculty.chiba-u.jp.
■
1-(2-(Methylsulfinyl)phenyl)-2-phenylethane-1,2-dione (4):
yellow crystals (hexane−chloroform); mp 115.0−116.8 °C; 1H
NMR (300 MHz, CDCl3) δ 3.12 (s, 3H), 7.52 (t, J = 7.3 Hz, 2H),
7.66 (t, J = 7.5 Hz, 1H), 7.71−7.79 (m, 3H), 8.01 (dd, J = 2.1 and 7.8
Notes
The authors declare no competing financial interest.
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Note
two reactions depicted in Scheme 2 were conducted in CHCl3 with a
same quality.
ACKNOWLEDGMENTS
■
This work was partially supported by the Iodine Research
Project at Chiba University.
(16) Unfortunately, it seemed not to exclude a contamination of
molecular oxygen completely even under precious conditions (see the
Experimental Section). But, in the case of the reaction under “sealed
conditions”, unidentified product(s) was observed, which suggests the
decease of ratio of α-diketones formation.
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(14) Relative intensity of MS: [M]+ = 256 (5.40) and [M + 2]+ = 258
(0.58) for 2 formed with H218O, and [M]+ = 256 (5.32) and [M + 2]+
= 258 (0.36) for 2 formed without H218O. [M + H]+ = 273 (100) and
[M + H + 2]+ = 275 (4.41) for 3 formed with H218O, and [M + Na]+
= 295 (100), [M + Na + 2]+ = 297 (4.22), and [M + H]+ = 273 (3.31)
for 3 formed without H218O ([M + H + 2]+ = 275 was not observed).
Confer: [M] = 288 (0.32) and [M + 2] = 290 (0.90) for 4 formed with
H218O, and [M] = 288 (1.91) and [M + 2] = 290 (0.14) for 4 formed
without H218O. Mass spectra were obtained with EI for 2 and 4, but
with ESI for 3 because of the lack of observation of the parent ion peak
by measuring 3 with EI method.
(15) The different yield against entry 2 in Table 1 would be caused
by the difference of the amount of adventitious water in CHCl3. The
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